Flame retardant resin composition and molded articles thereof

ABSTRACT

A flame retardant resin composition consisting essentially of:
     (A) 100 parts by weight of the total of resin components (components A) which include at least 60 wt % of an aromatic polyester resin;   (B) an organic phosphorus compound (component B-1) represented by the following general formula (1) and having an acid value of 0.7 mgKOH/g or less or an organic phosphorus compound (component B-2) represented by the following general formula (2);   (C) 0 to 50 parts by weight of a flame retardancy improving resin (component C); and   (D) 0 to 200 parts by weight of a filler (component D), and a molded article thereof.   

     Wherein, when the organic phosphorus compound is the component B-1, the amount of the component B-1 is 1 to 100 parts by weight and when the organic phosphorus compound is the component B-2, the component B-2 is used in combination with a biscumyl compound (component B-3), the amount of the component B-2 is 5 to 30 parts by weight, and the amount of the component B-3 is 0.01 to 5 parts by weight. 
     
       
         
         
             
             
         
       
     
     According to the present invention, there can be obtained a flame retardant polyester resin composition which contains substantially no halogen and has UL-94 V-2 flame retardancy or V-0 flame retardancy under favorable conditions as well as a molded article thereof.

The present application is a Continuation application of Ser. No.10/476,390, filed Oct. 31, 2003 (which is a 371 application ofPCT/JP02/04659, filed May 14, 2002), now U.S. Pat. No. 7,087,667.

DETAILED DESCRIPTION OF THE INVENTION

1. Field of the Invention

The present invention relates to a flame retardant polyester resincomposition having high flame retardancy and excellent physicalproperties and to molded articles formed therefrom. More specifically,it relates to a substantially halogen-free flame retardant polyesterresin composition which comprises a specific organic phosphorus compoundas a flame retardant and to molded articles formed therefrom.

2. Prior Art

Thermoplastic aromatic polyester resins including polybutyleneterephthalate (to be abbreviated as PBT hereinafter) are widely used asmolded articles for use in electric and electronic, mechanical part andautomobile fields as they have excellent mechanical properties, heatresistance, chemical resistance and the like.

Among these application fields are a large number of fields whichrequire flame retardancy and there have been provided resins whichcomprise a halogen-containing compound and an antimony compound as aflame retardant and a flame retardant aid, respectively, to achieveflame retardancy.

However, a decomposed product of a halogen-containing flame retardantmay corrode a metal contained in an electric product and further somehalogen-containing flame retardants are now in question from theviewpoint of their influence upon environment. Therefore, a strong trendtoward use of halogen-free resin molded articles is seen mainly inEurope. Demand for halogen-free flame retardants is growing and thedevelopment of a halogen-free flame retardant to be contained in resinsis under way vigorously. Technologies for flame retarding polyesterresins with halogen-free flame retardants have been reported but are notimplemented yet because they still have various problems to be solved.

In general, a phosphorus-containing compound is often used as ahalogen-free flame retardant, as exemplified by phosphates such as redphosphorus and triphenyl phosphate (to be abbreviated as TPPhereinafter) in the field of the present invention. However, a polyesterresin such as PBT has a relatively high processing temperature and redphosphorus generates a highly toxic phosphine gas. When red phosphorusis used, the resulting composition becomes brown due to red phosphorus,resulting in its limited use. Meanwhile, low-molecular weight TPP has ableed-out problem and an aromatic phosphate typified by TPP generallyhas a plasticizing effect, thereby greatly reducing the heat resistanceof the obtained composition.

Known documents on technologies for improving flame retardant resincompositions comprising a phosphorus-containing compound as a flameretardant are introduced hereinbelow. For example, JP-A 7-126498 (theterm “JP-A” as used herein means an “unexamined published Japanesepatent application”) discloses a halogen-free flame retardant for apolyester resin, which is obtained by melt reacting a polyester resin,an epoxy compound having two or more epoxy groups in the molecule and aphenolic resin and/or phosphorus-, nitrogen- or boron-based compoundhaving a functional group which can react with an epoxy group. JP-A7-278267 discloses a flame retardant polyester resin composition whichcomprises 5 to 50 parts by weight of the above halogen-free flameretardant and 100 parts by weight of a polyester resin. However, theabove resin composition is still unsatisfactory in terms of flameretardancy, inferior in fluidity and economically disadvantageous.

JP-A 8-208884 discloses a flame retardant resin composition obtained byadding a phosphorus-containing compound (specifically triphenylphosphate) such as a phosphate or phosphite and an ortho- orpara-substituted phenolic resin to a thermoplastic resin such aspolystyrene or polyester. This resin composition has problems such asbleed-out and a reduction in heat resistance and cannot achievesufficiently high flame retardancy.

JP-B 2-37370 (the term “JP-B” as used herein means an “examined Japanesepatent publication”) discloses a flame retardant polyester resincomposition which comprises 99 to 34 parts by weight of a thermoplasticpolyester resin having a softening point of 150° C. or higher, such aspolyethylene terephthalate, 1 to 25 parts by weight of red phosphoruscoated with a thermosetting resin and 10 to 55 parts by weight of areinforcing filler. However, this resin composition has problems such ascoloring and the generation of phosphine gas during molding as describedabove.

Further, JP-A 50-58319 discloses a flame retardant polyester fibercomposition which comprises a fiber forming linear polyester, arylspirophosphate and halogen-containing flame retardant containing atleast 40% of chlorine atom or bromine atom. This publication shows theflame retardancy of a fiber prepared by blending polyethyleneterephthalate with an aryl spirophosphate and a halogen-containingcompound as flame retarding components.

JP-A 52-12329 (German Patent 2630693 and English Patent 1515223) teachesthat flame retardancy is developed by blending a specific organicphosphorus-containing compound with a polyester fiber. Morespecifically, the publication discloses an example in which a fiber isobtained by mixing polyethylene terephthalate with a specific organicphosphorus compound and a fabric formed of the fiber has slightlyimproved flame retardancy (for example, oxygen index). The technologydisclosed by this publication merely teaches the flame retardation of apolyethylene terephthalate fiber.

U.S. Pat. No. 3,866,405 discloses a flame retardant fiber compositionwhich comprises a specific polyester resin and a halogen-containingspirodiphosphate. This publication shows the flame retardancy of a fiberobtained by blending a spirodiphosphate containing elemental halogenwith a polyethylene naphthalate resin. However, this US patent relatesto a fiber and a halogen-containing flame retardant is used, thusinvolving an environmental problem as described above, thoughimprovement in the flame retardancy of the polyester fiber is seen.

U.S. Pat. No. 4,257,931 discloses a flame retardant resin compositionwhich comprises a polyester resin, melamine pyrophosphate and organiccyclic phosphorus compound. In this publication, a high flame retardingeffect is obtained by using the above two flame retardants. Althoughthis flame retarding effect is mainly obtained from the melaminepyrophosphate, when this melamine pyrophosphate is used, the appearanceof a molded article of the composition becomes poor. Therefore, it isdifficult to put this composition to practical use.

JP-A 2000-103972 discloses a composition obtained by flame retarding athermoplastic resin such as styrene-based resin, polyester resin,polyamide resin or polycarbonate resin. This publication teaches thattwo flame retardants consisting of an aromatic phosphate and a specificphosphorus compound are used in specific amounts and that a radicalgenerating agent or phenolic resin is used in combination with theseflame retardants. However, as flame retardancy achieved by thecomposition of this publication is V-2, high flame retardancy is notobtained yet. Since use of an aromatic phosphate is essential to thiscomposition, a bleed-out problem arises and a molded article of thecomposition deteriorates in hydrolytic resistance.

JP-A 2000-103973 discloses a flame retardant resin composition preparedby blending a thermoplastic resin with a specific phosphorus compoundand a phenolic resin as essential flame retardants and a flame retardantresin composition prepared by further blending a fluorine-containingresin or a radical generating agent with this composition. However, thecomposition of this publication attains V-0 flame retardancy when itcomprises ABS resin, AS resin, PPE resin, polystyrene resin orpolycarbonate resin. There is no description in this publication of aflame retardant resin composition comprising a polyester resin.

Problems to be Solved by the Invention

It is a first object of the present invention to provide a polyesterresin composition which has high flame retardancy and good balancebetween heat resistance and mechanical properties useful for industrialpurposes as well as molded articles formed therefrom.

It is a second object of the present invention to provide a polyesterresin composition which can attain high flame retardancy, that is, UL-94V-2 or higher, or V-0 or higher in favorable conditions substantiallywithout containing halogen as well as molded articles formed therefrom.

It is a third object of the present invention to provide a flameretardant polyester resin composition which can be advantageously usedin home electric appliance parts, electric and electronic parts,mechanical parts and auto parts as well as molded articles formedtherefrom.

It is a fourth object of the present invention to provide a flameretardant composition having excellent transparency.

It is a fifth object of the present invention to provide a flameretardant which is a novel organic phosphorus compound.

Means to Solve the Problems

According to researches conducted by the inventors of the presentinvention, the above objects of the present invention are attained by aflame retardant resin composition consisting essentially of:

-   (A) 100 parts by weight of the total of resin components    (components A) which include at least 60 wt % of an aromatic    polyester resin;-   (B) an organic phosphorus compound (component B-1) represented by    the following general formula (1) and having an acid value of 0.7    mgKOH/g or less or an organic phosphorus compound (component B-2)    represented by the following general formula (2);-   (C) 0 to 50 parts by weight of a flame retardancy improving resin    (component C); and-   (D) 0 to 200 parts by weight of a filler (component D), and molded    articles formed therefrom.

When the organic phosphorus compound is component B-1, the amount of thecomponent B-1 is 1 to 100 parts by weight. When the organic phosphoruscompound is component B-2, the component B-2 is used in combination witha biscumyl compound (component B-3) represented by the following generalformula (3), the amount of the component B-2 is 5 to 30 parts by weight,and the amount of the component B-3 is 0.01 to 5 parts by weight.

(wherein X₁ and X₂ are the same or different and each an aromaticsubstituted alkyl group represented by the formula -(AL)-(Ar)_(n) (AL isa branched or linear aliphatic hydrocarbon group having 1 to 5 carbonatoms, Ar is a phenyl group, napthyl group or anthryl group, n is aninteger of 1 to 3, and Ar may be bonded to any carbon atom of AL).)

(wherein R¹ to R⁸ may be the same or different and each a hydrogen atom,alkyl group having 1 to 12 carbon atoms, alkyloxy group having 1 to 12carbon atoms, alkylthio group having 1 to 12 carbon atoms or grouprepresented by Ar³—Y— (Y is —O—, —S— or alkylene group having 1 to 8carbon atoms, and Ar³ is an aryl group having 6 to 15 carbon atoms).)

(wherein R⁹ to R¹⁸ may be the same or different and each a hydrogenatom, alkyl group having 1 to 12 carbon atoms, alkyloxy group having 1to 12 carbon atoms, alkylthio group having 1 to 12 carbon atoms or grouprepresented by Ar³—Y— (Y is —O—, —S— or alkylene group having 1 to 8carbon atoms, and Ar³ is an aryl group having 6 to 15 carbon atoms).)

According to the present invention, there is obtained a flame retardantpolyester resin composition which has excellent mechanical propertiesand at least V-2 flame retardancy, or V-0 flame retardancy in favorableconditions.

The flame retardant resin composition of the present invention will bedescribed in more detail hereinunder.

As for the resin components in the present invention, an aromaticpolyester resin must be the main component among the resin components(components A). That is, the aromatic polyester resin (component A-1)may be contained in an amount of preferably at least 60 wt %, morepreferably at least 70 wt %, particularly preferably at least 80 wt %.Another resin (component A-2) may be contained in an amount of less than40 wt %, preferably less than 30 wt %, particularly preferably less than20 wt % of the total of all the components A. This another resin will bedescribed in detail hereinafter.

The aromatic polyester resin (component A-1) out of the resin components(components A) of the present invention is a polyester which comprisesan aromatic dicarboxylic acid as the main dicarboxylic acid componentand an aliphatic diol having 2 to 10 carbon atoms as the main glycolcomponent. The aromatic dicarboxylic acid is contained in an amount ofpreferably 80 mol % or more, more preferably 90 mol % or more based onthe total of all the dicarboxylic acid components. The aliphatic diolhaving 2 to 10 carbon atoms is contained in an amount of preferably 80mol % or more, more preferably 90 mol % or more based on the total ofall the glycol components.

Preferred examples of the aromatic dicarboxylic acid component includeterephthalic acid, isophthalic acid, phthalic acid, methylterephthalicacid, methylisophthalic acid and 2,6-naphthalenedicarboxylic acid. Theymay be used alone or in combination of two or more. Dicarboxylic acidsother than the aromatic dicarboxylic acids include aliphaticdicarboxylic acids and alicyclic dicarboxylic acids such as adipic acid,sebacic acid, decanedicarboxylic acid, azelaic acid,dodecanedicarboxylic acid and cyclohexanedicarboxylic acid.

Examples of the aliphatic diol having 2 to 10 carbon atoms includealiphatic diols such as ethylene glycol, trimethylene glycol,tetramethylene glycol, hexamethylene glycol and neopentyl glycol, andalicyclic diols such as 1,4-cyclohexane dimethanol. Glycols other thanthe aliphatic diols having 2 to 10 carbon atoms includep,p′-dihydroxyethoxybisphenol A and polyoxyethylene glycol.

The aromatic polyester resin (component A-1) is preferably a polyesterhaving an ester unit which comprises at least one dicarboxylic acidselected from terephthalic acid and 2,6-naphthalenedicarboxylic acid asthe main dicarboxylic acid component and at lest one diol selected fromethylene glycol, trimethylene glycol and tetramethylene glycol as themain diol component.

The aromatic polyester resin (component A-1) is preferably at least oneselected from the group consisting of polyethylene terephthalate-resin,polybutylene terephthalate resin, polyethylene naphthalate resin,polybutylene naphthalate resin, polycyclohexanedimethyl terephthalateresin, polytrimethylene terephthalate resin and polytrimethylenenaphthalate resin.

It is particularly preferably at least one selected from the groupconsisting of polyethylene terephthalate resin, polybutyleneterephthalate resin and polyethylene naphthalate resin. It is ideallypolybutylene terephthalate resin.

The aromatic polyester resin (component A-1) of the present inventionmay be a polyester elastomer which comprises the above recurring unit asthe main recurring unit of a hard segment.

The soft segment of a polyester elastomer comprising tetramethyleneterephthalate or tetramethylene-2,6-naphthalene dicarboxylate as themain recurring unit of a hard segment is a polyester or polycaprolactonewhich comprises at least one dicarboxylic acid selected fromterephthalic acid, isophthalic acid, sebacic acid and adipic acid and atleast one diol selected from the group consisting of a long-chain diolhaving 5 to 10 carbon atoms and H(OCH₂CH₂)_(i)OH (i=2 to 5) and whichhas a melting point of 100° C. or lower or noncrystallinity.

The main component is a component which is contained in an amount of 80mol % or more, preferably 90 mol % or more based on the total of all thedicarboxylic acid components or all the glycol components, and the mainrecurring unit is contained in an amount of 80 mol % or more,preferably-90 mol % or more based on the total of all the recurringunits.

As for the molecular weight of the aromatic polyester resin in thepresent invention, the aromatic polyester resin may have an intrinsicviscosity that enables it to be used as an ordinary molded article,preferably 0.5 to 1.6 dl/g, more-preferably 0.6 to 1.5 dl/g whenmeasured in orthochlorophenol at 35° C.

It is advantageous that the aromatic polyester resin have a terminalcarboxyl group (—COOH) in an amount of 1 to 60 equivalents/t (1 ton of apolymer). The amount of this terminal carboxyl group can be obtained bya potential difference titration method using an m-cresol solution ofthe aromatic polyester resin and an alkali solution.

The constituent resins (components A) of the present invention mayinclude another thermoplastic resin (component A-2) other than the abovearomatic polyester resin (component A-1). As described above, the amountof the another resin (component A-2) is less than 40 wt %, preferablyless than 30 wt % based on the total of all the components A.

The thermoplastic resin as the component A-2 is at least one selectedfrom the group consisting of polyphenylene ether resin (PPE),polycarbonate resin (PC), polyamide resin (PA), polyolefin resin (PO),polystyrene-based resin, polyphenylene sulfide resin (PPS) and polyetherimide resin (PEI). Out of these components A-2, polyphenylene etherresin (PPE), polycarbonate resin (PC), polyamide resin (PA), polyolefinresin (PO) and polystyrene-based resin are preferred.

A description is subsequently given of the thermoplastic resin as thecomponent A-2.

As the polyphenylene ether resin as the component A-2 may be used whatis generally known as PPE resin. Examples of the PPE resin includehomopolymers and/or copolymers such as(2,6-dimethyl-1,4-phenylene)ether, (2,6-diethyl-1,4-phenylene)ether,(2,6-dipropyl-1,4-phenylene)ether,(2-methyl-6-ethyl-1,4-phenylene)ether,(2-methyl-6-propyl-1,4-phenylene)ether and(2,3,6-trimethyl-1,4-phenylene)ether.Poly(2,6-dimethyl-1,4-phenylene)ether is particularly preferred.Copolymers obtained by graft polymerizing the above PPE with a styrenecompound may also be used. The process for producing PPE is notparticularly limited. For instance, PPE can be easily manufactured byoxidation polymerizing 2,6-xylenol in the presence of a complex of acuprous salt and an amine as a catalyst in accordance with the processof U.S. Pat. No. 3,306,874.

The reduced viscosity ηsp/C (0.5 g/dl, toluene solution, measured at 30°C.) which is an index of the molecular weight of the PPE resin is 0.2 to0.7 dl/g, preferably 0.3 to 0.6 dl/g. PPE resin having a reducedviscosity within the above range has good balance between moldabilityand mechanical properties. The reduced viscosity of the PPE resin can beeasily adjusted by controlling the amount of a catalyst and the like forthe production of PPE.

The polycarbonate-based resin (PC) as the component A-2 is obtained byan interfacial polymerization reaction between a dihydroxyaryl compoundand phosgene in the presence of a solvent such as methylene chloride oran ester exchange reaction between a dihydroxyaryl compound and diphenylcarbonate. It is typically a polycarbonate obtained by a reactionbetween 2,2′-bis(4-hydroxyphenyl)propane and phosgene.

Examples of the dihydroxyaryl compound as a raw material of thepolycarbonate include bis(4-hydroxyphenyl)methane,1,1′-bis(4-hydroxyphenyl)ethane, 2,2′-bis(4-hydroxyphenyl)propane,2,2′-bis(4-hydroxyphenyl)butane, 2,2′-bis(4-hydroxyphenyl)octane,2,2′-bis(4-hydroxyphenyl-3-methylphenyl)propane,2,2′-bis(4-hydroxyphenyl-3-t-butylphenyl)propane,2,2′-bis(3,5-dimethyl-4-hydroxyphenyl)propane,2,2′-bis(4-hydroxy-3-cyclohexylphenyl)propane,2,2′-bis(4-hydroxy-3-methoxyphenyl)propane,1,1′-bis(4-hydroxyphenyl)cyclopentane,1,1′-bis(4-hydroxyphenyl)cyclohexane,1,1′-bis(4-hydroxyphenyl)cyclododecane, 4,4′-dihydroxyphenyl ether,4,4′-dihydroxy-3,3′-dimethylphenyl ether, 4,4′-dihydroxydiphenylsulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide,4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone andbis(4-dihydroxydiphenyl)ketone. These dihydroxyaryl compounds may beused alone or in combination of two or more.

The dihydroxyaryl compound is preferably a bisphenol which forms anaromatic polycarbonate having high heat resistance,bis(hydroxyphenyl)alkane such as 2,2′-bis(4-hydroxyphenyl)propane,bis(hydroxyphenyl)cycloalkane such as bis(4-hydroxyphenyl)cyclohexane,dihydroxydiphenyl sulfide, dihydroxydiphenyl sulfone ordihydroxydiphenyl ketone. The dihydroxyaryl compound is particularlypreferably 2,2′-bis(4-hydroxyphenyl)propane which forms a bisphenol Aaromatic polycarbonate.

Part of bisphenol A may be substituted by another dihydroxyaryl compoundto produce the bisphenol A aromatic polycarbonate as far as it does notimpair heat resistance and mechanical strength.

The molecular weight of the polycarbonate resin does not need to beparticularly limited but if it is too low, the strength of thepolycarbonate resin becomes unsatisfactory and if it is too high, themelt viscosity becomes too high, thereby making it difficult to mold thepolycarbonate resin. Therefore, the viscosity average molecular weightof the polycarbonate resin is generally 10,000 to 50,000, preferably15,000 to 30,000. The viscosity average molecular weight (M) as usedherein is obtained by inserting a specific viscosity (η_(sp)) obtainedfrom a solution of 0.7 g of a polycarbonate resin dissolved in 100 ml ofmethylene chloride at 20° C. into the following expression.η_(sp) /C=[η]+0.45×[η]² C[η]=1.23×10⁻⁴M^(0.83)C=0.7([η] is an intrinsic viscosity and C is the concentration of thepolymer)

A brief description is given of the basic means of producing thepolycarbonate resin. In the interfacial polycondensation method(solution polymerization method) using phosgene as a carbonateprecursor, a reaction is generally carried out in the presence of anacid binder and an organic solvent. Examples of the acid binder includealkali metal hydroxides such as sodium hydroxide and potassiumhydroxide, and amine compounds such as pyridine. Examples of the organicsolvent include halogenated hydrocarbons such as methylene chloride andchlorobenzene. A catalyst such as a tertiary amine or quaternaryammonium compound may be used to promote the reaction, and a terminalcapping agent such as an alkyl-substituted phenol exemplified by phenoland p-tert-butylphenol is desirably used as a molecular weight controlagent. The reaction temperature is generally 0 to 40° C., the reactiontime is several-minutes to 5 hours, and pH during the reaction ispreferably maintained at 10 or more. All the terminals of the obtainedmolecular chain do not need to have a structure derived from theterminal capping agent.

In the ester exchange reaction (melt polymerization method) using acarbonic diester as a carbonate precursor, a diphenol and a carbonicdiester are stirred in a predetermined ratio under heating in thepresence of an inert gas to distill out the formed alcohol or phenol.The reaction temperature which changes according to the boiling point orthe like of the formed alcohol or phenol is generally 120 to 350° C. Thereaction is completed while the alcohol or phenol formed under vacuumfrom the beginning of the reaction is distilled off. A terminal cappingagent is added together with the diphenol in the initial stage of thereaction or during the reaction. A catalyst used for a known esterexchange reaction can be used to promote the reaction. Examples of thecarbonic diester used for this ester exchange reaction include diphenylcarbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonateand dibutyl carbonate. Out of these, diphenyl carbonate is particularlypreferred.

The polyamide resin (PA) as the component A-2 is, for example, aring-opening polymer of a cyclic lactam, a polymer of an aminocarboxylicacid or a polycondensate of a dibasic acid and a diamine. Specificexamples of the polyamide resin include aliphatic polyamides such asnylon 6, nylon 66, nylon 46, nylon 610, nylon 612, nylon 11 and nylon12, aliphatic-aromatic polyamides such as poly(metaxylene adipamide),poly(hexamethylene terephthalamide), poly(nonamethyleneterephthalamide), poly(hexamethylene isophthalamide) andpoly(tetramethylene isophthalamide), and copolymers and mixturesthereof. The polyamide which can be used in the present invention is notlimited to a particular kind.

Although the molecular weight of the polyamide resin is not particularlylimited, the relative viscosity measured in 98% sulfuric acid at aconcentration of 1% and 25° C. of the polyamide resin is 1.7 to 4.5,preferably 2.0 to 4.0, particularly preferably 2.0 to 3.5.

The polyolefin resin as the component A-2 is a homopolymer or copolymerof an olefin such as ethylene, propylene or butane, or a copolymer of anolefin and a monomer copolymerizable with the olefin. Specific examplesof the polyolefin resin include polyethylene, polypropylene,ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer,ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer,ethylene-α-olefin copolymer, ethylene-propylene copolymer andethylene-butene copolymer. The molecular weight of the polyolefin resinis not particularly limited but a polyolefin resin having a highermolecular weight has higher flame retardancy.

The styrene-based resin as the component A-2 is a homopolymer orcopolymer of an aromatic vinyl monomer such as styrene, α-methylstyreneor vinyl toluene, copolymer of one of the above monomers and a vinylmonomer such as acrylonitrile or methyl methacrylate, or graft polymerobtained by graft polymerizing diene-based rubber such as polybutadiene,ethylene.propylene-based rubber or acrylic rubber with styrene and/orstyrene derivative, or styrene and/or styrene derivative with anothervinyl monomer. Specific examples of the styrene-based resin includepolystyrene, high-impact polystyrene (HIPS), acrylonitrile.styrenecopolymer (AS resin), acrylonitrile.butadiene.styrene copolymer (ABSresin), methyl methacrylatebutadiene-styrene copolymer (MBS resin),methyl methacrylate.acrylonitrile.butadiene.styrene copolymer (MABSresin), acrylonitrile.acrylic rubber.styrene copolymer (AAS resin),acrylonitrile.ethylene propylene-based rubber.styrene copolymer (AESresin), and mixtures thereof. From the viewpoint of impact resistance, arubber modified styrene-based resin is preferred and is a polymer whichcontains rubber-like polymer particles dispersed in a matrix composed ofa vinyl aromatic polymer and which is obtained by the known bulkpolymerization, bulk suspension-polymerization, solution polymerizationor emulsion polymerization of an aromatic vinyl monomer or a monomermixture of an aromatic vinyl monomer and a vinyl monomer in the presenceof a rubber-like polymer.

Examples of the rubber-like polymer include diene-based rubbers such aspolybutadiene, poly(styrene-butadiene) andpoly(acrylonitrile-butadiene), saturated rubbers obtained byhydrogenating the above diene-based rubbers, acrylic rubbers such asisoprene rubber, chloroprene rubber and butyl polyacrylate, andethylene-propylene-diene monomer terpolymer (EPDM). Diene-based rubbersare particularly preferred.

The aromatic vinyl monomer as an essential component of a graftcopolymerizable monomer mixture which is polymerized in the presence ofthe above rubber-like polymer is, for example, styrene, α-methylstyreneor paramethylstyrene and the most preferably styrene.

The vinyl monomer which can be added optionally is acrylonitrile ormethyl methacrylate.

The amount of the rubber-like polymer in the rubber modified styreneresin is 1 to 50 wt %, preferably 2 to 40 wt %. The amount of the graftpolymerizable monomer mixture is 99 to 50 wt %, preferably 98 to 60 wt%.

The polyphenylene sulfide resin (PPS) as the component A-2 has arecurring unit represented by the following formula:

wherein n is an integer of 1 or more, preferably 50 to 500, morepreferably 100 to 400.The polyphenylene sulfide resin may be linear or crosslinked.

To produce the polyphenylene sulfide resin, dichlorobenzene and sodiumdisulfide are reacted with each other. To produce a crosslinkedpolyphenylene sulfide resin, a polymer having a low degree ofpolymerization is polymerized and heated in the presence of air to carryout partial crosslinking so as to increase the molecular weight. Toproduce a linear polyphenylene sulfide resin, the molecular weight ofthe resin is increased during polymerization.

The polyether imide resin (PEI) as the component A-2 has a recurringunit represented by the following formula.

Ar¹ in the above formula is the aromatic dihydroxy compound residue andAr² is the aromatic diamine residue. Examples of the aromatic dihydroxycompound are aromatic dihydroxy compounds enumerated in the explanationof the polycarbonate resin, out of which bisphenol A is particularlypreferred. Examples of the aromatic diamine include m-phenylenediamine,p-phenylenediamine, 4,4′-diaminodiphenyl, 3,4′-diaminodiphenyl,4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, diaminodiphenylmethane, diaminodiphenyl sulfone and diaminodiphenyl sulfide.

In the above formula, n is an integer of 5 to 1,000, preferably 10 to500.

Processes for producing the polyether imide resin are disclosed by U.S.Pat. No. 3,847,867, U.S. Pat. No. 3,847,869, U.S. Pat. No. 3,850,885,U.S. Pat. No. 3,852,242 and U.S. Pat. No. 3,855,178.

Out of the above components A-2, polyphenylene ether resin (PPE),polycarbonate resin (PC), polyamide resin (PA) and polystyrene-basedresin are preferred.

The flame retardant resin compositions of the present invention areroughly divided into two types according to an organic phosphoruscompound (component B) used as a flame retardant. One is a flameretardant resin composition (I) which comprises the component B-1 as anorganic phosphorus compound and the other is a flame retardant resincomposition (II) which comprises the component B-2 as an organicphosphorus compound. The flame retardant resin compositions (I) and (II)of the present invention are outlined hereinbelow.

Flame Retardant Resin Composition (I)

This is a flame retardant resin composition consisting essentially of:

-   (A) 100 parts by weight of the total of resin components    (components A) which include at least 60 wt % of an aromatic    polyester resin;-   (B) 1 to 100 parts by weight of an organic phosphorus compound    (component B-1) represented by the following general formula (1) and    having an acid value of 0.7 mgKOH/g or less;-   (C) 0 to 50 parts by weight of a flame retardancy improving resin    (component C); and-   (D) 0 to 200 parts by weight of a filler (component D):

wherein X₁ and X₂ are the same or different and each an aromaticsubstituted alkyl group represented by -(AL)-(Ar)_(n) (AL is a branchedor linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, Ar isa phenyl group, naphthyl group or anthryl group, n is an integer of 1 to3, and Ar may be bonded to any carbon atom of AL).Flame Retardant Resin Composition (II)

This is a flame retardant resin composition consisting essentially of(A) 100 parts by weight of the total of resin components (components A)which include at least 60 wt % of an aromatic polyester resin, (B) 5 to30 parts by weight of an organic phosphorus compound (component B-2)represented by the following general formula (2) and 0.01 to 5 parts byweight of a biscumyl compound (component B-3) represented by thefollowing general formula (3), (C) 0 to 50 parts by weight of a flameretardancy improving resin (component C) and (D) 0 to 200 parts byweight of a filler (component D):

wherein R¹ to R⁸ may be the same or different and each a hydrogen atom,alkyl group having 1 to 12 carbon atoms, alkyloxy group having 1 to 12carbon atoms, alkylthio group having 1 to 12 carbon atoms or grouprepresented by Ar³—Y— (Y is —O—, —S— or alkylene group having 1 to 8carbon atoms, and Ar³ is an aryl group having 6 to 15 carbon atoms),

wherein R⁹ to R¹⁸ may be the same or different and each a hydrogen atom,alkyl group having 1 to 12 carbon atoms, alkyloxy group having 1 to 12carbon atoms, alkylthio group having 1 to 12 carbon atoms or grouprepresented by Ar³—Y— (Y is —O—, —S— or alkylene group having 1 to 8carbon atoms, and Ar³ is an aryl group having 6 to 15 carbon atoms).

The above flame retardant resin compositions (I) and (II) of the presentinvention will be described in detail. A description is first given ofthe composition (I).

In the composition (I), the organic phosphorus compound (component B-1)represented by the following general formula (1) is used as a flameretardant.

In the above formula, X₁ and X₂ are the same or different and each anaromatic substituted alkyl group represented by -(AL)-(Ar)_(n). AL is abranched or linear aliphatic hydrocarbon group having 1 to 5 carbonatoms, preferably 1 or 2 carbon atoms. Specifically, AL is preferably

Ar is a phenyl group, naphthyl group or anthryl group, preferably phenylgroup. n is an integer of 1 to 3, preferably 1 or 2. Ar may be bonded toany carbon atom of AL.

The organic phosphorus compound (component B-1) represented by the aboveformula (1) exhibits an extremely excellent flame retarding effect foran aromatic polyester resin. As far as the inventors of the presentinvention know, in the halogen-free flame retardation of a conventionalaromatic polyester resin, V-0 flame retardancy could not be attained byusing a phosphorus compound alone. To attain V-0 flame retardancy byusing a phosphorus compound, use of a flame retardant aid orcarbonization promoting substance or use of different types of flameretardants was essential. According to the present invention,surprisingly, an aromatic polyester resin can easily attain V-0 flameretardancy by using the above organic phosphorus compound (componentB-1) alone. However, in the present invention, besides the componentB-1, a flame retardancy improving resin, phosphorus compound other thanthe component B-1, fluorine-containing resin, filler or other additivesmay be used to reduce the amount of the component B-1, improve the flameretardancy of a molded article, improve the physical properties of amolded article, or improve the chemical properties of a molded articleas a matter of course. These components are described in detailhereinafter.

The organic phosphorus compound (component B-1) as a flame retardant inthe flame retardant resin composition (I) of the present invention isrepresented by the above general formula (1). The most preferred typicalcompound is at least one selected from compounds represented by thefollowing formulas (1-a) to (1-d). These compounds may be used alone orin combination of two or more.

Out of these compounds represented by the above formulas (1-a) to (1-d),the component B-1-a represented by the formula (1-a) or the componentB-1-c represented by the formula (1-c) are preferred from the viewpointof a flame retarding effect or synthesis ease.

A description is subsequently given of the method of synthesizing theabove organic phosphorus compound (component B-1) in the presentinvention. The component B-1 may be produced by a method other than thefollowing methods.

The component B-1 is obtained by reacting pentaerythritol withphosphorus trichloride, treating the oxidized reaction product with analkali metal compound such as sodium methoxide and reacting the reactionproduct with an aralkyl halide.

The component B-1 may also be obtained by reacting pentaerythritol withan aralkylphosphonic acid dichloride or by reacting pentaerythritol withphosphorus trichloride to obtain a compound, reacting the compound withan aralkyl alcohol and then carrying out Arbuzov transfer at a hightemperature. The latter reactions are disclosed by U.S. Pat. No.3,141,032, JP-A 54-157156 and JP-A 53-39698.

The method of synthesizing the component B-1 is described hereinbelow.This method is merely described for explanation and the component B-1used in the present invention may be synthesized not only by this methodbut also by modifying the method and other methods. The methods aredetailed in Preparation Examples 1 to 9.

(i) Organic Phosphorus Compound of the Formula (1-a) Out of theComponents B-1;

A reaction product obtained by reacting pentaerythritol with phosphorustrichloride and oxidizing with tertiary butanol is treated with sodiummethoxide and further reacted with benzyl bromide.

(ii) Organic Phosphorus Compound of the Formula (1-b) Out of theComponents B-1;

A reaction product obtained by reacting pentaerythritol with phosphorustrichloride and oxidizing with tertiary butanol is treated with sodiummethoxide and reacted with 1-bromoethylbenzene.

(iii) Organic Phosphorus Compound of the Formula (1-c) Out of theComponents B-1;

A reaction product obtained by reacting pentaerythritol with phosphorustrichloride and oxidizing with tertiary butanol is treated with sodiummethoxide and reacted with 2-bromoethylbenzene.

(iv) Organic Phosphorus Compound of the Formula (1-d) Out of theComponents B-1;

This can be obtained by reacting pentaerythritol with diphenylmethylphosphonic acid dichloride.

The above components B-1 have an acid value of 0.7 mgKOH/g or less,preferably 0.5 mgKOH/g or less. A molded article which has excellentflame retardancy and color and also a molded article which hardlyexperiences the decomposition of a polyester resin and has excellentheat stability are obtained by using the component B-1 having an acidvalue within the above range. A component B-1 having an acid value of0.4 mgKOH/g or less is the most preferred. The acid value means theamount (mg) of KOH required to neutralize an acid component contained in1 g of a sample (component B-1).

Further, the component B-1 has an HPLC purity of preferably at least90%, more preferably at least 95%. The component B-1 having the abovepurity is preferred because it provides a molded article havingexcellent flame retardancy and color. The HPLC purity of the componentB-1 can be effectively measured by the following method.

The Develosil ODS-7 column having a length of 300 mm and a diameter of 4mm of Nomura Kagaku Co., Ltd. was used and the column temperature was40° C. The solvent was a mixed solution of acetonitrile and water in avolume ratio of 6:4 and injected in an amount of 5 μl. A UV-260 nmdetector was used.

The method of removing impurities contained in the component B-1 is notparticularly limited but a method in which repulp cleaning (cleaningwith a solvent and filtration are repeated several times) is carried outwith a solvent such as water or methanol is the most effective andeconomically advantageous.

The above component B-1 is contained in an amount of 1 to 100 parts byweight, preferably 5 to 90 parts by weight, more preferably 10 to 70parts by weight based on 100 parts by weight of the total of the resincomponents (components A). The amount of the component B-1 isparticularly preferably 15 to 50 parts by weight. A preferred range ofthe amount of the component B-1 is determined by desired flameretardancy rating, the types of the resin components (components A), thetype and amount of the filler, and the like. Further, the amount of thecomponent B-1 can be changed by using a flame retardancy improvingresin, other flame retardant or fluorine-containing resin. In mostcases, the amount of the component B-1 can be reduced by using the abovecomponents.

A description is subsequently given of the flame retardancy improvingresin (component C) which may be contained in the flame retardant resincomposition (I) of the present invention. The flame retardancy can beimproved by blending the component C. The flame retardancy improvingresin is preferably a phenolic resin (component C-i), epoxy resin(component C-ii) or styrene-based resin (component C-iii). Thecomponents C-i, C-ii and C-iii are described in detail hereinbelow.

Any phenolic resin may be used as the component C-i if it ismacromolecular with a plurality of phenolic hydroxyl groups. Examples ofthe phenolic resin include novolak, resol and heat reactive resins, andmodified resins thereof. They may be uncured resins without a curingagent, semi-cured resins or cured resins. Out of these, non-reactivephenol novolak resins without a curing agent are particularly preferredin terms of flame retardancy, impact resistance and economicalefficiency. The shape of the phenolic resin is not particularly limitedand may be powdered, particulate, flaky, powdery, needle-like or liquid.The above phenolic resins may be used alone or in combination of two ormore as required.

The phenolic resin is not particularly limited and may be a commerciallyavailable general phenolic resin. For example, to obtain a novolakphenolic resin, a phenol and an aldehyde are charged into a reactor in amolar ratio of 1:0.7 to 1:0.9, a catalyst such as oxalic acid,hydrochloric acid, sulfuric acid or toluenesulfonic acid is added, andthen heating and a reflux reaction are carried out. Vacuum dehydrationor standing dehydration is carried out to remove the formed water, andfurther the residual water and unreacted phenol are removed to obtainthe phenolic resin. A condensation phenolic resin can be obtained from aplurality of raw material components and can be used as well.

To obtain a resol phenolic resin, a phenol and an aldehyde are chargedinto a reactor in a molar ratio of 1:1 to 1:2, a catalyst such as sodiumhydroxide, ammonia water or other basic substance is added, and the sameoperation as the novolak phenolic resin is carried out.

Examples of the phenol include phenol, o-cresol, m-cresol, p-cresol,thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol,o-methoxyphenol, 4,4′-dihydroxyphenylpropane, isoamyl salicylate, benzylsalicylate, methyl salicylate and 2,6-di-tert-butyl-p-cresol. Thesephenols may be used alone or in combination of two or more as required.Examples of the aldehyde include formaldehyde, paraformaldehyde,polyoxymethylene and trioxan. These aldehydes may be used alone or incombination of two or more as well.

The molecular weight of the phenolic resin is not particularly limitedbut a phenolic resin having a number average molecular weight ofpreferably 200 to 2,000, more preferably 400 to 1,500 is excellent inmechanical properties, moldability and economic efficiency.

Examples of the epoxy resin used as the component C-ii include bisphenolA epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin,bisphenol S epoxy resin, phenol novolak epoxy resin, cresol novolakepoxy resin, naphthalene epoxy resin and bisphenol epoxy resin. Theepoxy resin is not limited to these. These epoxy resins may be usedalone or in combination of two or more, or modified.

The styrene-based resin used as the component C-iii which is a flameretardancy improving resin is a homopolymer or copolymer of an aromaticvinyl monomer such as styrene, α-methylstyrene or vinyltoluene, or acopolymer of one of the above monomers and a vinyl monomer. Thestyrene-based resin as the component C-iii contains the above aromaticvinyl monomer component in an amount of 50 wt % or more, preferably 60wt % or more, particularly preferably 70 wt % or more.

Specific examples of the styrene-based resin as the component C-iiiinclude polystyrene, high-impact polystyrene (HIPS),acrylonitrile.styrene copolymer (AS resin),acrylonitrile.butadiene.styrene copolymer (ABS resin), methylmethacrylate.butadiene.styrene copolymer (MBS resin), methylmethacrylate.acrylonitrile.butadiene.styrene copolymer (MABS resin),acrylonitrile.acrylic rubber.styrene copolymer (AAS resin),acrylonitrile.ethylene propylene-based rubber.styrene copolymer (AESresin) and mixtures thereof.

When the above flame retardancy improving resin (component C) is used,the amount of the component C is 0.01 to 45 parts by weight, preferably0.1 to 40 parts by weight, particularly preferably 0.5 to 35 parts byweight based on 100 parts by weight of the total of the components A.When the component C is the component C-iii, the amount thereof is 0.01to 10 parts by weight, preferably 0.1 to 5 parts by weight based on 100parts by weight of the total of the components A. Even when the amountof the component C-iii is so small, flame retardancy is greatlyimproved.

The flame retardant resin composition (I) of the present invention maycomprise a filler (component D). The filler may be used to improve thephysical properties, particularly mechanical properties of a moldedarticle and may be inorganic or organic. It is preferably a fibrousfiller.

Examples of the filler (component D) include glass-based fillers such asglass chopped fiber, glass milled fiber, glass roving strand, glassflake, glass bead and glass powder; carbon-based fillers such as carbonfiber, carbon milled fiber, carbon roving strand and carbon flake;inorganic fillers such as talc, mica, wollastonite, kaolin,montmorillonite, bentonite, sepiolite, xonotlite, clay and silica;organic fillers such as aramide fiber; inorganic pigments such astitanium oxide, and carbon black. They may be used alone or incombination of two or more. To reinforce the resin composition, afibrous filler such as a glass fiber, carbon fiber or mixture thereof ispreferably used.

The inorganic filler may be optionally treated with a binder or surfacetreating agent before use. The type of the binder agent or surfacetreating agent is not particularly limited but a functional compoundsuch as an epoxy-based compound, silane-based compound or titanate-basedcompound is suitably selected according to the resin. An epoxy-basedcompound is preferred, and bisphenol A and/or novolak epoxy resin(s)are/is more preferred.

When the above filler (component D) is used, the amount thereof is 1 to200 parts by weight, preferably 1 to 150 parts by weight, morepreferably 1 to 100 parts by weight based on 100 parts by weight of thetotal of the above resin components (components A). When the amount islarger than 200 parts by weight, the flame retardancy and physicalproperties of the resin composition deteriorate and the operation easeand moldability of the resin composition lower disadvantageously.

The flame retardant resin composition (I) of the present invention maycomprise a fluorine-containing resin (component E). The flame retardancyof a molded article is improved by blending the component E.Particularly, dripping in the burning test of a molded article issuppressed.

The fluorine-containing resin used as the component E is notparticularly limited if it has fibril forming capability. Thefluorine-containing resin is a homopolymer or copolymer of afluorine-containing monomer such as tetrafluoroethylene,trifluoroethylene, vinyl fluoride, vinylidene fluoride orhexafluoropropylene. It is particularly preferablypolytetrafluoroethylene having fibril forming capability. Thepolytetrafluoroethylene having fibril forming capability is, forexample, a powder obtained by coagulating and drying a latex obtained byemulsion polymerizing tetrafluoroethylene (so-called fine powder ofpolytetrafluoroethylene and classified ASTM type 3). Or it is an aqueousdispersion produced by adding a surfactant to the latex andconcentrating and stabilizing it (so-called dispersion ofpolytetrafluoroethylene).

The molecular weight of the polytetrafluoroethylene having fibrilforming capability is 1,000,000 to 10,000,000, more preferably 2,000,000to 9,000,000 in terms of number average molecular weight obtained fromstandard specific gravity.

The polytetrafluoroethylene having fibril forming capability has aprimary particle diameter of preferably 0.05 to 1.0 μm, more preferably0.1 to 0.5 μm. When a fine powder is used, its secondary particlediameter is 1 to 1,000 μm, preferably 10 to 500 μm.

The polytetrafluoroethylene has flaming drip preventing capability whenits specimen is burnt in a UL vertical burning test. Specific examplesof the polytetrafluoroethylene having fibril forming capability includeTeflon 6J and Teflon 30J of Mitsui•Du Pont Fluorochemical Co., Ltd.,Polyfuron MPA FA-500, Polyfuron F-201L and Polyfuron D-1 of DaikinKagaku Kogyo Co., Ltd., and CD076 of Asahi ICI Fluoropolymers Co., Ltd.

A fine powder of polytetrafluoroethylene which has been subjected to atreatment for the prevention of secondary agglomeration is morepreferred. The treatment is the baking of the surface ofpolytetrafluoroethylene. Or it is the coating of the surface ofpolytetrafluoroethylene having fibril forming capability withpolytetrafluoroethylene having no fibril forming capability.Polytetrafluoroethylene subjected to the latter treatment is morepreferred in the present invention. In the former case, the targetedfibril forming capability is apt to deteriorate. In this case, theamount of polytetrafluoroethylene having no fibril forming capability ispreferably 70 to 95 wt %. The number average molecular weight obtainedfrom standard specific gravity of polytetrafluoroethylene having fibrilforming capability is 10,000 to 1,000,000, preferably 10,000 to 800,000.

The polytetrafluoroethylene (may be abbreviated as PTFE hereinafter) maybe used in the form of an aqueous dispersion besides a solid form asdescribed above.

Although the polytetrafluoroethylene may be used in the form of anaqueous emulsion or dispersion besides a normal solid form, thepolytetrafluoroethylene in a solid form is particularly preferably usedbecause a dispersant is apt to exert a bad influence upon moist heatresistance.

An agglomerated mixture of an emulsion of the polytetrafluoroethylenehaving fibril forming capability and an emulsion of a vinyl-basedpolymer is also preferably used to improve dispersibility in a resin andobtain a better appearance and higher mechanical properties.

Examples of the vinyl-based polymer include polypropylene, polyethylene,polystyrene, HIPS, AS resin, ABS resin, MBS resin, MABS resin, AASresin, polymethyl (meth)acrylate, block copolymers of styrene andbutadiene, hydrogenated copolymers thereof, block copolymers of styreneand isoprene, hydrogenated copolymers thereof, acrylonitrile-butadienecopolymer, ethylene-propylene random copolymer and block copolymer,ethylene-butene random copolymer and block copolymer, ethylene-α-olefincopolymers, ethylene-unsaturated carboxylate copolymers such asethylene-butyl acrylate copolymer, acrylate-butadiene copolymers such asbutyl acrylate-butadiene copolymer, rubber-like polymers such aspolyalkyl (meth)acrylate, composite rubbers containingpolyorganosiloxane and polyalkyl (meth)acrylate, and copolymers obtainedby graft polymerizing one of the composite rubbers with a vinyl-basedmonomer such as styrene, acrylonitrile or polyalkyl methacrylate.

To prepare the agglomerated mixture, an aqueous emulsion of the abovevinyl-based polymer having an average particle diameter of 0.01 to 1 μm,particularly 0.05 to 0.5 μm is mixed with an aqueous emulsion ofpolytetrafluoroethylene having an average particle diameter of 0.05 to10 μm, particularly 0.05 to 1.0 μm. The emulsion ofpolytetrafluoroethylene is obtained by emulsion polymerizingpolytetrafluoroethylene in the presence of a fluorine-containingsurfactant. A comonomer such as hexafluoropropylene may be copolymerizedin an amount of 10 wt % or less based on polytetrafluoroethylene for theabove emulsion polymerization.

To obtain the agglomerated mixture, a suitable polytetrafluoroethyleneemulsion having a solid content of generally 40 to 70 wt %, particularly50 to 65 wt % and a suitable vinyl-based polymer emulsion having a solidcontent of 25 to 60 wt %, particularly 30 to 45 wt % are used. Further,the amount of polytetrafluoroethylene in the agglomerated mixture ispreferably 1 to 80 wt %, particularly preferably 1 to 60 wt % based on100 wt % of the total of the polytetrafluoroethylene and the vinyl-basedpolymer used in the agglomerated mixture. After the above emulsions aremixed together, they are stirred and injected into hot water containinga metal salt such as calcium chloride or magnesium sulfate to separateand collect the above agglomerated mixture through salting-out andsolidification. Alternatively, the stirred and mixed emulsions may bespray dried or freeze dried to collect the agglomerated mixture.

The agglomerated mixture of the emulsion of polytetrafluoroethylenehaving fibril forming capability and the emulsion of the vinyl-basedpolymer may be various in form. For example, eachpolytetrafluoroethylene particle is coated with the vinyl-based polymer,the vinyl-based polymer is coated with polytetrafluoroethylene, orseveral particles agglomerate around one particle.

Further, the same or different type of a vinyl-based polymer may begraft polymerized on the outer layer of the agglomerated mixture.Preferred examples of the vinyl-based monomer include styrene,α-methylstyrene, methyl methacrylate, cyclohexyl acrylate, dodecylmethacrylate, dodecyl acrylate, acrylonitrile and 2-ethylhexyl acrylate.They may be used alone or copolymerized.

Typical commercially available products of the agglomerated mixture ofthe emulsion of polytetrafluoroethylene having fibril forming capabilityand the emulsion of the vinyl-based polymer include the Metabrene A3000of Mitsubishi Rayon Co., Ltd. and the BLENDEX449 of GE SpecialtyChemicals Co., Ltd.

When the component E is used, the amount thereof is preferably 0.01 to10 parts by weight, more preferably 0.1 to 5 parts by weight based on100 parts by weight of the total of the components A. Below 0.01 part byweight, sufficient flaming drip prevention capability is easily obtainedand above 10 parts by weight, a poor appearance may be hardly obtainedor a dispersion failure may rarely occur, and it is economicallyadvantageous.

Some embodiments of the flame retardant resin composition (I) of thepresent invention are described hereinbelow.

One of the embodiments is a flame retardant resin composition (I) whichconsists essentially of the following components (A) to (E). Thecomposition of this embodiment contains a fluorine-containing resin ascomponent E and has an excellent drip preventing effect in the burningtest of a molded article.

-   (A) 100 parts by weight of the total of resin components    (components A) which include at least 60 wt % of an aromatic    polyester resin,-   (B) 1 to 100 parts by weight of an organic phosphorus compound    (component B-1) represented by the above general formula (1) and    having an acid value of 0.7 mgKOH/g or less,-   (C) 0 to 50 parts by weight of a flame retardancy improving resin    (component C),-   (D) 0 to 200 parts by weight of a filler (component D), and-   (E) 0.01 to 10 parts by weight of a fluorine-containing resin    (component E).

Another embodiment is a flame retardant resin composition which consistsessentially of the following components (A) to (E) and has a heatstability (MVR change rate) of 20% or less, preferably 15% or less, morepreferably 10% or less, particularly preferably 5% or less. Thecomposition of this embodiment provides excellent heat stability(especially heat stability of mechanical strength) to a molded articledue to the high purity (especially acid value or HPLC purity) of thecomponent B-1. The heat stability is measured by a method which isdescribed hereinafter.

-   (A) 100 parts by weight of the total of resin components    (components A) which include at least 60 wt % of an aromatic    polyester resin,-   (B) 1 to 100 parts by weight of an organic phosphorus compound    (component B-1) represented by the above general formula (1),-   (C) 0 to 50 parts by weight of a flame retardancy improving resin    (component C),-   (D) 0 to 200 parts by weight of a filler (component D), and-   (E) 0 to 10 parts by weight of a fluorine-containing resin    (component E).

Still another embodiment is a flame retardant resin composition whichconsists essentially of the following components (A), (B), (C) and (E)and has transparency with a total light transmittance of 80% or more,preferably 83% or more, more preferably 85% or more. The composition ofthis embodiment provides a molded article containing substantially nofiller and having high transparency. Since the organic phosphoruscompound as the component B-1 is an achromatic powder and has excellentcompatibility with the resin components A, a molded article of thiscomposition has excellent transparency and when a pigment or dye isadded, a transparent molded article having a bright color is obtained.

-   (A) 100 parts by weight of the total of resin components    (components A) which include at least 60 wt % of an aromatic    polyester resin,-   (B) 1 to 100 parts by weight of an organic phosphorus compound    (component B-1) represented by the above general formula (1) and    having an acid value of 0.7 mgKOH/g or less,-   (C) 0 to 50 parts by weight of a flame retardancy improving resin    (component C), and-   (E) 0 to 10 parts by weight of a fluorine-containing resin    (component E).

The above flame retardant resin composition (I) of the present inventioncontains substantially no halogen and attains V-2 flame retardancy as amatter of course, V-0 flame retardancy in most embodiments. A 1.6mm-thick molded article of the composition (I) of the present inventioncan attain UL-94 V-0 flame retardancy. Even a 0.8 mm-thick moldedarticle of the composition (I) can attain V-0 flame retardancy underfavorable conditions.

A description is subsequently given of the flame retardant resincomposition (II) of the present invention. The flame retardant resincomposition (II) consists essentially of the following components (A) to(D).

That is, the flame retardant resin composition consists essentially of(A) 100 parts by weight of the total of resin components (components A)which include at least 60 wt % of an aromatic polyester resin, (B) 5 to30 parts by weight of an organic phosphorus compound (component B-2)represented by the following general formula (2) and 0.01 to 5 parts byweight of a biscumyl compound (component B-3) represented by thefollowing general formula (3), (C) 0 to 50 parts by weight of a flameretardancy improving resin (component. C) and (D) 0 to 200 parts byweight of a filler (component D):

wherein R¹ to R⁸ may be the same or different and each a hydrogen atom,alkyl group having 1 to 12 carbon atoms, alkyloxy group having 1 to 12carbon atoms, alkylthio group having 1 to 12 carbon atoms or grouprepresented by Ar³—Y— (Y is —O—, —S— or alkylene group having 1 to 8carbon atoms, and Ar³ is an aryl group having 6 to 15 carbon atoms),

wherein R⁹ to R¹⁸ may be the same or different and each a hydrogen atom,alkyl group having 1 to 12 carbon atoms, alkyloxy group having 1 to 12carbon atoms, alkylthio group having 1 to 12 carbon atoms or grouprepresented by Ar³—Y— (Y is —O—, —S— or alkylene group having 1 to 8carbon atoms, and Ar³ is an aryl group having 6 to 15 carbon atoms).

The above flame retardant resin composition (II) is characterized inthat it comprises both of the components B-2 and B-3 as flameretardants. In this composition (II), the resin components (componentsA), flame retardancy improving resin (component C), filler (component D)and fluorine-containing resin (component E) are identical to thosedescribed in the above flame retardant resin composition (I), andpreferred components are also identical. The composition (I) and thecomponent (II) are common in the amount of each component and thepreferred range of the amount of each component. Therefore, detaileddescriptions of the components A, C, D and E of the composition (II) areomitted. The components B-2 and B-3 are described hereinbelow.

The flame retardants in the flame retardant resin composition (II) arethe organic phosphorus compound (component B-2) represented by the abovegeneral formula (2) and the biscumyl compound (component B-3)represented by the above general formula (3).

The organic phosphorus compound (component B-2) of the above generalformula (2) is a 6H-benzo[c,e][1,2]oxaphospholin-6-one derivative. Thetwo benzene rings of this compound may each have 1 to 4 substituents,preferably 1 to 2 substituents. The substituents (R¹ to R⁸) are selectedfrom (i) alkyl groups having 1 to 12 carbon atoms, preferably alkylgroups having 1 to 9 carbon atoms such as methyl group, ethyl group,propyl group, isopropyl group, n-butyl group, sec-butyl group,tert-butyl group, neopentyl group and nonyl group, (ii) alkyloxy groupshaving 1 to 12 carbon atoms, preferably alkyloxy groups having 1 to 9carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxygroup and pentoxy group, (iii) alkylthio groups having 1 to 12 carbonatoms, preferably alkylthio groups having 1 to 9 carbon atoms such asmethylthio group, ethylthio group, propylthio group, butylthio group andpentylthio group, and (iv) groups represented by Ar³—Y— (Y is —O—, —S—or alkylene group having 1 to 8 carbon atoms, preferably 1 to 4 carbonatoms, and Ar³ is an aryl group having 6 to 15 carbon atoms, preferably6 to 10 carbon atoms). The component B-2 is particularly preferably anorganic phosphorus compound in which R¹ to R⁸ are all hydrogen atomsbecause it is easily acquired.

The organic phosphorus compound as the component B-2 can be generallyobtained by thermally condensing phosphorus trichloride with ano-phenylphenol compound in the presence of a Friedel-Crafts catalyst andcarrying out hydrolysis. This reaction is disclosed by JP-A 47-16436,JP-A 7-145185 and JP-A 10-1490, and this method is preferably employed.

The two benzene rings of the biscumyl compound (component B-3) of theabove general formula (3) may have 1 to 5 substituents, preferably 1 to3 substituents, respectively. The substituents are selected from (i)alkyl groups having 1 to 12 carbon atoms, (ii) alkyloxy groups having 1to 12 carbon atoms, (iii) alkylthio groups having 1 to 12 carbon atomsand (iv) groups represented by Ar³—Y— like substituents in the abovegeneral formula (2). The component B-3 is economically particularlypreferably a (biscumyl) compound in which R⁹ to R¹⁸ are all hydrogenatoms because it is easily acquired.

In the composition (II), the amount of the component B-2 is 5 to 30parts by weight, preferably 6 to 25 parts by weight, more preferably 7to 20 parts by weight based on 100 parts by weight of the total of theresin components (components A). Below 5 parts by weight, the obtainedresin composition is inferior in flame retardancy and above 30 parts byweight, the resin composition deteriorates in physical properties and itis economically disadvantageous.

The amount of the component B-3 is 0.01 to 5 parts by weight, preferably0.02 to 4 parts by weight, more preferably 0.03 to 3 parts by weightbased on 100 parts by weight of the total of the resin components(components A). Below 0.01 part by weight, the obtained resincomposition is inferior in flame retardancy and above 0.5 parts byweight, the resin composition deteriorates in physical properties andflame retardancy and it is economically disadvantageous.

It is advantageous that the total amount of the components B-2 and B-3in the composition (II) be 6 to 33 parts by weight, preferably 7 to 30parts by weight based on 100 parts by weight of the total of thecomponents A and that the weight ratio of the component B-2 to thecomponent B-3 be 4/1 to 70/1, preferably 5/1 to 60/1.

The composition (II) contains substantially no halogen and can attainUL-94 V-0 flame retardancy for a 1.6 mm-thick molded article, or 0.8mm-thick molded article under favorable conditions.

The components A, B (B-1, B-2 and B-3), C, D and E constituting theflame retardant resin compositions (I) and (II) of the present inventionhave already been described. Components other than the above componentsmay be used optionally in limits that do not impair the object of thepresent invention. The other components which can be added to thecompositions (I) and (II) are described hereinbelow.

(1) Phosphorus or Phosphorus Compound (Component F);

Phosphorus or a phosphorus compound (component F) known per se may beused as a flame retardant in the compositions (I) and (II) besides theorganic phosphorus compound (component B). When the component F is usedin conjunction with the component B, a flame retarding effect, physicalstrength and heat resistance can be improved and cost can be furtherreduced.

Examples (F-1) to (F-4) of the component F are given below.

(F-1); red phosphorus

(F-2); a triaryl phosphate represented by the following general formula(F-2)

(F-3); a condensation phosphate represented by the following generalformula (F-3)

(F-4); a condensation phosphate represented by the following generalformula (F-4)

Q¹ to Q⁴ in the above formulas (F-2) to (F-4) may be the same ordifferent and each an aryl group having 6 to 15 carbon atoms, preferablyaryl group having 6 to 10 carbon atoms. Examples of the aryl groupinclude phenyl group, naphthyl group and anthryl group. The aryl groupmay have 1 to 5 substituents, preferably 1 to 3 substituents. Thesubstituents are selected from (i) alkyl groups having 1 to 12 carbonatoms, preferably alkyl groups having 1 to 9 carbon atoms such as methylgroup, ethyl group, propyl group, isopropyl group, n-butyl group,sec-butyl group, tert-butyl group, neopentyl group and nonyl group, (ii)alkyloxy groups having 1 to 12 carbon atoms, preferably alkyloxy groupshaving 1 to 9 carbon atoms such as methoxy group, ethoxy group, propoxygroup, butoxy group and penthoxy group, (iii) alkylthio groups having 1to 12 carbon atoms, preferably alkylthio groups having 1 to 9 carbonatoms such as methylthio group, ethylthio group, propylthio group,butylthio group and pentylthio group, and (iv) groups represented byAr⁶—W¹— (W¹ is —O—, —S— or alkylene group having 1 to 8 carbon atoms,preferably 1 to 4 carbon atoms, and Ar⁶ is an aryl group having 6 to 15carbon atoms, preferably 6 to 10 carbon atoms).

In the formulas (F-3) and (F-4), Ar⁴ and Ar⁵ may be the same ordifferent and each an arylene group having 6 to 15 carbon atoms,preferably arylene group having 6 to 10 carbon atoms when both of themare existent (in the case of F-4). Examples of Ar⁴ and Ar⁵ includephenylene group and naphthylene group. The arylene group may have 1 to 4substituents, preferably 1 to 2 substituents. The substituents areselected from (i) alkyl groups having 1 to 4 carbon atoms such as methylgroup, ethyl group, propyl group, isopropyl group, n-butyl group,sec-butyl group and tert-butyl group, (ii) aralkyl groups having 7 to 20carbon atoms such as benzyl group, phenethyl group, phenylpropyl group,naphthylmethyl group and cumyl group, (iii) groups represented by Q⁵-W²—(W² is —O— or —S—, and Q⁵ is an alkyl group having 1 to 4 carbon atoms,preferably 1 to 3 carbon atoms or aryl group having 6 to 15 carbonatoms, preferably 6 to 10 carbon atoms), and (iv) aryl groups having 6to 15 carbon atoms such as phenyl group.

In the formulas (F-3) and (F-4), m is an integer of 1 to 5, preferably 1to 3, particularly preferably 1.

In the formula (F-4), Z is a single bond or group for linking Ar⁴ andAr⁵, and —Ar⁴-Z-Ar⁵— is the residue derived from bisphenol. Accordingly,Z is a single bond, —O—, —CO—, —S—, —SO₂— or alkylene group having 1 to3 carbon atoms, preferably single bond, —O— or isopropylidene.

A phosphorus compound other than phosphorus and phosphorus compounds ofthe above formulas (F-1) to (F-4) may be used in combination with thecomponent B. For example, the component B-2 may be used in thecomposition (I) and the component B-1 may be used in the composition(II).

When phosphorus or a phosphorus compound (component F) of one of theabove formulas (F-1) to (F-4) is blended with the resin composition, theamount thereof is preferably 1 to 100 parts by weight, more preferably 5to 80 parts by weight, particularly preferably 10 to 60 parts by weightbased on 100 parts by weight of the organic phosphorus compound(component B). Out of the phosphorus and phosphorus compounds of theformulas (F-1) to (F-4), phosphorus compounds of the formulas (F-2) to(F-4) are preferred.

(2) Flame Retardant Aid;

A known flame retardant aid may be further blended with the flameretardant resin compositions (I) and (II) of the present invention. Theflame retardant aid is, for example, a silicone oil. The silicone oil isa polydiorganosiloxane, preferably polydiphenylsiloxane,polymethylphenylsiloxane, polydimethylsiloxane, or a copolymer ormixture thereof. Out of these, polydimethylsiloxane is preferred. Theviscosity of the silicone oil is preferably 0.8 to 5,000 cp (25° C.),more preferably 10 to 1,000 cp (25° C.), particularly preferably 50 to500 cp (250° C.). A flame retardant aid having a viscosity within theabove range has excellent flame retardancy. The amount of the siliconeoil is preferably 0.5 to 10 parts by weight based on 100 parts by weightof the total of the resin components (components A).

(3) Compatibilizing Agent;

A compatibilizing agent may be optionally added to the flame retardantresin compositions (I) and (II) of the present invention. Thecompatibilizing agent is not limited to a particular kind and preferablycan compatibilize polymers as well as resin components such as thecomponents A and/or the component C with other additives when a mixtureof the components A-1 and A-2 is used or the component A and thecomponent C are used as a mixture of two or more components. Not onlythe mechanical properties but also the flame retardancy of the flameretardant resin compositions (I) and (II) of the present invention canbe improved by adding the compatibilizing agent. The amount of thecompatibilizing agent is not particularly limited but may be such thatit does not impair the object of the present invention.

(4) Additives;

Additives such as deterioration preventing agents including antioxidant,ultraviolet light absorber and optical stabilizer, lubricant, antistaticagent, release agent, plasticizer and colorant (pigment) may be added tothe flame retardant resin compositions (I) and (II) of the presentinvention. The amounts of the above additives can be suitably selectedaccording to the types and purposes of the additives in limits that donot impair flame retardancy, heat resistance, impact resistance andmechanical strength.

As for the preparation of the flame retardant resin compositions (I) and(II) of the present invention, preferably, the resin components(components A), organic phosphorus compound (component B) and optionallyother components are pre-mixed together by a mixer such as twin-cylindermixer, super mixer, super floater or Henschel mixer, and the obtainedpre-mixture is supplied to a kneader to be melt kneaded. The kneader isa melt mixer such as kneader, or a single-screw or double-screwextruder. Out of these, a double-screw extruder is used to melt a resincomposition at 220 to 280° C., preferably 230 to 270° C., liquidcomponents are injected by a side feeder, and the obtained product isextruded and pelletized by a pelletizer.

The flame retardant resin compositions (I) and (II) of the presentinvention contain substantially no halogen, have extremely high flameretardancy and are useful as molding materials for producing variousmolded articles such as home electric appliance parts, electric andelectronic parts, auto parts, mechanical and structural parts, andcosmetic containers. Stated more specifically, they can beadvantageously used in breaker parts, switch parts, motor parts,ignition coil cases, power plugs, power outlets, coil bobbins,connectors, relay cases, fuse cases, flyback transformer parts, focusblock parts, distributor caps and harness connectors. They are alsouseful in housings, casings and chassis which are being reduced inthickness, such as housings or casings and chassis for electronic andelectric products (for example, home electric appliances and OAequipment such as telephones, personal computers, printers, facsimiles,copiers, video decks and audio equipment, and their parts). They areparticularly useful for housings for printers, fixing unit parts, andmechanical and constituent parts of home electric appliances and OAequipment such as facsimiles which require high heat resistance andflame retardancy.

The molding technique is not particularly limited and may be injectionmolding, blow molding or press molding. Preferably, a molded article ispreferably produced by injection molding a pellet-like resin compositionwith an injection molding machine.

The organic phosphorus compound of the formula (1-d) out of thecomponents B-1 used in the flame retardant resin composition (I) of thepresent invention is a novel compound as far as the inventors of thepresent invention know and was provided by the inventors of the presentinvention and used as a flame retardant for the first time.

According to the present invention, there are provided a flame retardantwhich is an organic phosphorus compound represented by the followingformula (1-d) and a flame retardant resin composition which comprisesthe organic phosphorus compound in an effective amount as a flameretardant. The organic phosphorus compound of the formula (1-d) can beused as a flame retardant for a polyester resin but is expected to havethe same effect as a flame retardant for other resins.

EXAMPLES

The following examples are provided for the purpose of furtherillustrating the present invention but are in no way to be taken aslimiting. Evaluations were made by the following methods.

(1) Flame Retardancy (UL-94 Ratings)

Flame retardancy was evaluated using 1/16-inch (1.6 mm) and 1/32-inch(0.8 mm) thick test pieces in accordance with a vertical burning testspecified in UL-94 of the US UL standards as an index for evaluatingflame retardancy. The flame retardancy of each test piece is classifiedV-0 when combustion ceases within 10 seconds after the removal of flamesand flaming drips do not ignite cotton, V-2 when combustion ceaseswithin 30 seconds and flaming drips ignite cotton, and not V when flameretardancy is below the above criteria.

(2) Flame Retardancy (OI Test)

This was evaluated in accordance with JIS-K-7201. As the numerical valueincreases, the flame retardancy becomes higher.

(3) Acid Value

This was measured in accordance with JIS-K-3504.

(4) MVR (Fluidity Test)

This was measured in accordance with ISO-1133.

(5) Heat Stability (MVR Change Rate)

The pellet was treated at 130° C. for 24 hours. MVR of the pellet wasmeasured under a load of 3.8 kg at 230° C. before and after thetreatment to obtain its change rate from the following expression.ΔY=(|Y ₂ −Y ₁ |/Y ₁)×100(%)Y₁: MVR before treatment (cm³/10 in)Y₂: MVR after treatment (cm³/10 min)

Preparation examples of the organic phosphorus compound used in Examplesare given below.

Preparation Example 1 Preparation of2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-dibenzyl-3,9-dioxide (FR-1)

6.81 parts of pentaerythritol, 0.16 part of pyridine and 8.65 parts oftoluene were charged into a reactor equipped with a thermometer,capacitor and dropping funnel to be stirred. 13.76 parts of phosphorustrichloride was added to the reactor using the dropping funnel andstirred under heating at 60° C. After a reaction, the reactor was cooledto room temperature, 26.50 parts of methylene chloride was added to theobtained reaction product, and 7.42 parts of tertiary butanol and 1.25parts of methylene chloride were added dropwise under cooling with ice.The obtained crystals were cleaned with toluene and methylene chlorideand then filtered. The obtained filtrate was dried at 80° C. and1.33×10² Pa for 12 hours to produce 10.76 parts of a white solid. It wasconfirmed from the ³¹P, ¹HNMR spectrum that the obtained solid was2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-dihydro-3,9-dioxide.

7.31 parts of 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-dihydro-3,9-dioxide and 47.22 parts of DMF were charged into areactor equipped with a thermometer, capacitor and dropping funnel to bestirred. 3.53 parts of sodium methoxide was added to the reactor undercooling with ice. They were stirred under cooling with ice for 2 hoursand further stirred at room temperature for 5 hours. After DMF wasdistilled off, 18.89 parts of DMF was added and 10.94 parts of benzylbromide was added dropwise to the reaction mixture under cooling withice. After 3 hours of agitation under cooling with ice, DMF wasdistilled off, and the residue was cleaned with water and methanol andthen filtered. The obtained filtrate was dried at 120° C. and 1.33×10²Pa for 19 hours to produce 10.15 parts of a white solid. It wasconfirmed from the ³¹P, ¹HNMR spectrum and elemental analysis that theobtained solid was 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-dibenzyl-3,9-dioxide. This compound had a yield of 78% and a ³¹PNMRpurity of 99%. It had an HPLC purity measured by the method of this textof 99%. It had an acid value of 0.06 mgKOH/g.

¹H-NMR (DMSO-d₆, 300 MHz): δ7.2-7.4 (m, 10H), 4.1-4.5 (m, 8H), 3.5 (d,4H), ³¹P-NMR (DMSO-d₆, 120 MHZ): δ23.1 (S), melting point: 255-256° C.,elemental analysis calculated values: C, 55.89; H, 5.43. measurementvalues: C, 56.24; H, 5.35.

Preparation Example 2 Preparation of2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-dibenzyl-3,9-dioxide (FR-2)

408.3 g (1.0 mol) of3,9-dibenzyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane and342.1 g (2.0 mol) of benzyl bromide were charged into a reactor equippedwith a stirrer, thermometer and capacitor, and dry nitrogen was causedto flow into the reactor under agitation at room temperature.Thereafter, heating was started with an oil bath which was kept at 150°C. for 10 minutes. The oil bath was removed to cool the reactor to roomtemperature. 2,000 ml of methanol was added to the obtained reactionproduct which was a white solid and stirred to clean the reactionproduct, and the white powder was separated by filtration with a glassfilter. Then, the separated white powder was cleaned with 2,000 ml of a50 wt % aqueous solution of methanol and dried at 100 Pa and 120° C. for8 hours to produce 334.6 g of bisbenzyl pentaerythritol diphosphonate.It was confirmed from mass spectral analysis, ¹H, ³¹P nuclear magneticresonance spectral analysis and elemental analysis that the product wasbisbenzyl pentaerythritol diphosphonate. This compound had a yield of82%, an HPLC purity of 99.2% and an acid value of 0.34 mgKOH/g.

¹H-NMR (DMSO-d₆, 300 MHz): δ7.2-7.4 (m, 10H), 4.1-4.5 (m, 8H), 3.5 (d,4H), ³¹P-NMR (DMSO-d₆, 120 MHz): δ23.1 (S), melting point: 257° C.

Preparation Example 3 Preparation of2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-dibenzyl-3,9-dioxide (FR-3)

6.81 parts of pentaerythritol, 0.16 part of pyridine and 8.65 parts oftoluene were charged into a reactor equipped with a thermometer,capacitor and dropping funnel to be stirred. 13.76 parts of phosphorustrichloride was added to the reactor using the dropping funnel andstirred under heating at 60° C. 10.82 parts of benzyl alcohol was addedto the obtained reaction mixture and stirred under heating. After theend of a reaction, 0.1 part of benzyl bromide was added, and the reactorwas sealed up and heated at 200° C. The reaction mixture was cooled withice, and the formed white solid was separated by filtration and driedunder vacuum at 100° C. and 1.33×10 Pa. It was confirmed from the ³¹P,¹HNMR spectrum that the obtained white solid was2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-dibenzyl-3,9-dioxide. The acid value of the solid was 2.5 mgKOH/g.

Preparation Example 4 Preparation of2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-diα-methylbenzyl-3,9-dioxide (FR-4)

6.81 parts of pentaerythritol, 0.16 part of pyridine and 8.65 parts oftoluene were charged into a reactor equipped with a thermometer,capacitor and dropping funnel to be stirred. 13.76 parts of phosphorustrichloride was added to the reactor using the dropping funnel andstirred under heating at 60° C. After a reaction, the reactor was cooledto room temperature, 26.50 parts of methylene chloride was added to theobtained reaction product, and 7.42 parts of tertiary butanol and 1.25parts of methylene chloride were added dropwise under cooling with ice.The obtained crystals were cleaned with toluene and methylene chlorideand filtered. The obtained filtrate was dried at 80° C. and 1.33×10² Pafor 12 hours to produce 10.76 g of a white solid. It was confirmed from³¹PNMR and ¹HNMR spectrum that the obtained solid was2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-dihydro-3,9-dioxide.

7.31 parts of the obtained2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-dihydro-3,9-dioxide and 47.22 parts of DMF were charged into areactor equipped with a thermometer, capacitor and dropping funnel to bestirred. 3.53 parts of sodium methoxide was added to the reactor undercooling with ice. After 2 hours of agitation under cooling with ice,they were stirred at room temperature for 5 hours. After DMF wasdistilled off, 18.89 parts of DMF was added, and 11.84 parts of(1-bromoethyl)benzene was added dropwise to the reaction mixture undercooling with ice. After 3 hours of agitation under cooling with ice, DMFwas distilled off, and the residue was cleaned with water and methanoland then filtered. The obtained filtrate was dried at 120° C. and1.33×10² Pa for 19 hours to produce 8.5 parts of a white solid. It wasconfirmed from ³¹PNMR, ¹HNMR spectrum and elemental analysis that theobtained solid was 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-diα-methylbenzyl-3,9-dioxide. This compound had a ³¹PNMR purity of99%. It had an HPLC purity measured by the method of this text of 99%and an acid value of 0.03 mgKOH/g.

¹H-NMR (CDCl₃, 300 MHz): δ7.2 to 7.4 (m. 10H), 4.0-4.2 (m, 4H), 3.4-3.8(m, 4H), 3.3 (qd, 4H), 1.6 (ddd, 6H), ³¹P-NMR (CDCl₃, 120 MHZ): δ28.7(S), melting point: 190-210° C., elemental analysis calculated values:C, 57.80; H, 6.01. measurement values: C, 57.83; H, 5.96.

Preparation Example 5 Preparation of2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-di(2-phenylethyl)-3,9-dioxide (FR-5)

6.81 parts of pentaerythritol, 0.16 part of pyridine and 8.65 parts oftoluene were charged into a reactor equipped with a thermometer,capacitor and dropping funnel to be stirred. 13.76 parts of phosphorustrichloride was added to the reactor using the dropping funnel andstirred under heating at 60° C. After a reaction, the reactor was cooledto room temperature, 26.50 parts of methylene chloride was added to theobtained reaction product, and 7.42 parts of tertiary butanol and 1.25parts of methylene chloride were added dropwise under cooling with ice.The obtained crystals were cleaned with toluene and methylene chlorideand then filtered. The obtained filtrate was dried at 80° C. and1.33×10² Pa for 12 hours to produce 10.76 parts of a white solid. It wasconfirmed from ³¹PNMR and ¹HNMR spectrum that the obtained solid was2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-dihydro-3,9-dioxide.

7.31 parts of the obtained2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-dihydro-3,9-dioxide and 47.22 parts of DMF were charged into areactor equipped with a thermometer, capacitor and dropping funnel to bestirred. 3.53 parts of sodium methoxide was added to the reactor undercooling with ice. After 2 hours of agitation under cooling with ice,they were stirred at room temperature for 5 hours. After DMF wasdistilled off, 18.89 parts of DMF was added, and 11.84 parts of(2-bromoethyl)benzene was added dropwise to the reaction mixture undercooling with ice. After 3 hours of agitation under cooling with ice, DMFwas distilled off, and the residue was cleaned with water and methanoland then filtered. The obtained filtrate was dried at 120° C. and1.33×10² Pa for 19 hours to produce 11.3 parts of a white solid. It wasconfirmed from ³¹PNMR, ¹HNMR spectrum and elemental analysis that theobtained solid was 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-di(2-phenylethyl)-3,9-dioxide. This compound had a ³¹PNMR purity of99%. It had an HPLC purity measured by the method of this text of 99%and an acid value of 0.03 mgKOH/g.

¹H-NMR (CDCl₃, 300 MHz): δ7.1-7.4 (m. 10H), 3.85-4.65 (m, 8H), 2.90-3.05(m, 4H), 2.1-2.3 (m, 4H), ³¹P-NMR (CDCl₃, 120 MHz): δ31.5 (S), meltingpoint: 245-246° C., elemental analysis calculated values: C, 57.80; H,6.01. measurement values: C, 58.00; H, 6.07.

Preparation Example 6 Preparation of2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-di(2-phenylethyl)-3,9-dioxide (FR-6)

436.4 g (1.0 mol) of3,9-di(2-phenylethoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecaneand 370.1 g (2.0 mol) of 2-phenylethyl bromide were charged into areactor equipped with a stirrer, thermometer and capacitor, and drynitrogen was caused to flow into the reactor under agitation at roomtemperature. Thereafter, heating was started with an oil bath which waskept at 180° C. for 10 hours. The oil bath was removed to cool thereactor to room temperature. 2,000 ml of methanol was added to theobtained reaction product which was a white solid and stirred to cleanthe reaction product, and the white powder was separated by filtrationwith a glass filter. Then, the separated white powder was cleaned with2,000 ml of a 50 wt % aqueous solution of methanol and dried at 100 Paand 120° C. for 8 hours to produce 362.3 g of2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-di(2-phenylethyl)-3,9-dioxide. It was confirmed from mass spectralanalysis, ¹H, ³¹P nuclear magnetic resonance spectral analysis andelemental analysis that the product wasbis-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-di(2-phenylethyl)-3,9-dioxide. This compound had a yield of 83%, anHPLC purity of 99.3% and an acid value of 0.41 mgKOH/g.

¹H-NMR (CDCl₃, 300 MHz): δ7.1-7.4 (m, 10H), 3.85-4.65 (m, 8H), 2.90-3.05(m, 4H), 2.1-2.3 (m, 4H), ³¹P-NMR (CDCl₃, 120 MHz): δ31.5 (S), meltingpoint: 245-246° C.

Preparation Example 7 Preparation of2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-bis(diphenylmethyl)-3,9-dioxide (FR-7)

2,058.5 g (7.22 mol) of diphenylmethylphosphonic acid dichloride, 468.1g (3.44 mol) of pentaerythritol, 1,169.4 g (14.8 mol) of pyridine and8,200 g of chloroform were charged into a 10-liter three-necked flaskequipped with a stirrer, agitating element, reflux condenser andthermometer, heated up to 60° C. in a nitrogen stream and stirred for 6hours. After the end of a reaction, chloroform was substituted bymethylene chloride, and 6 liters of distilled water was added to thereaction mixture and stirred to precipitate a white powder. The whitepowder was collected by suction filtration, and the obtained whiteproduct was cleaned with methanol and dried at 100° C. and 1.33×10² Pafor 10 hours to produce 1,156.2 g of a white solid. It was confirmedfrom ³¹P-NMR, ¹H-NMR spectrum and elemental analysis that the obtainedsolid was 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-bis(diphenylmethyl)-3,9-dioxide. This compound had a ³¹P-NMR purityof 99%. It had an HPLC purity measured by the method of this text of 99%and an acid value of 0.3 mgKOH/g.

¹H-NMR (DMSO-d₆, 300 MHz): δ7.20-7.60 (m, 20H), 5.25 (d, 2H), 4.15-4.55(m, 8H), ³¹P-NMR (DMSO-d₆, 120 MHz): δ20.9 (S), melting point: 265° C.,elemental analysis calculated values: C, 66.43; H, 5.39. measurementvalues: C, 66.14; H, 5.41.

Preparation Example 8 Preparation of2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-bis(diphenylmethyl)-3,9-dioxide (FR-8)

560.5 g (1.0 mol) of3,9-bis(diphenylmethoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecaneand 494.3 g (2.0 mol) of diphenylmethyl bromide were charged into areactor equipped with a stirrer, thermometer and capacitor, and drynitrogen was caused to flow into the reactor under agitation at roomtemperature. Thereafter, heating was started with an oil bath which waskept at 150° C. for 15 minutes. The oil bath was removed to cool thereactor to room temperature. 2,000 ml of acetone was added to theobtained reaction product which was a white solid and stirred to cleanthe reaction product, and the white powder was separated by filtrationwith a glass filter. Then, the separated white powder was cleaned with2,000 ml of a 50 wt % aqueous solution of methanol and dried at 100 Paand 120° C. for 8 hours to produce 398.0 g of2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-bis(diphenylmethyl)-3,9-dioxide. It was confirmed from mass spectralanalysis, ¹H, ³¹P nuclear magnetic resonance spectral analysis andelemental analysis that the product was2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-bis(diphenylmethyl)-3,9-dioxide. This compound had a yield of 71%,an HPLC purity of 99.1% and an acid value of 0.39 mgKOH/g.

¹H-NMR (DMSO-d6, 300 MHz): δ7.20-7.60 (m, 20H), 5.25 (d, 2H), 4.15-4.55(m, 8H), ³¹P-NMR (DMSO-d6, 120 MHz): δ20.9 (S), melting point: 264° C.

Preparation Example 9 Preparation of2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-bis(diphenylmethyl)-3,9-dioxide (FR-9)

560.5 g (1.0 mol) of3,9-bis(diphenylmethoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecaneand 494.3 g (2.0 mol) of diphenylmethyl bromide were charged into areactor equipped with a stirrer, thermometer and capacitor, and drynitrogen was caused to flow into the reactor under agitation at roomtemperature. Thereafter, heating was started with an oil bath which waskept at 150° C. for 15 minutes. The oil bath was removed to cool thereactor to room temperature. 2,000 ml of acetone was added to theobtained reaction product which was a white solid and stirred to cleanthe reaction product, and the white powder was separated by filtrationwith a glass filter. Then, the separated white powder was cleaned with2,000 ml of a 50 wt % aqueous solution of methanol and dried at 100 Paand 120° C. for 8 hours to produce 409.6 g of2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-bis(diphenylmethyl)-3,9-dioxide. It was confirmed from mass spectralanalysis, ¹H, ³¹P nuclear magnetic resonance spectral analysis andelemental analysis that the product was2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-bis(diphenylmethyl)-3,9-dioxide. This compound had a yield of 73%,an HPLC purity of 99.2% and an acid value of 0.63 mgKOH/g.

¹H-NMR (DMSO-d₆, 300 MHz): δ7.20-7.60 (m, 20H), 5.25 (d, 2H), 4.15-4.55(m, 8H), ³¹P-NMR (DMSO-d6, 120 MHz): δ20.9 (S), melting point: 264° C.

The following components were used in Examples and Comparative Examples.

(I) Polyester Resins (Component A-1)

-   (1) polybutylene terephthalate (TRB-H of Teijin Limited) (to be    referred to as PBT-1 hereinafter), MVR value measured under a load    of 3.8 kg at 230° C. of 9.5 cm³/10 min-   (2) polybutylene terephthalate (TRB-J of Teijin Limited) (to be    referred to as PBT-2 hereinafter), MVR value measured under a load    of 3.8 kg at 230° C. of 12.5 cm³/10 min-   (3) polyethylene terephthalate (TR-8580H of Teijin Limited) (to be    referred to as PET-1 hereinafter), MVR value measured under a load    of 1.2 kg at 280° C. of 42.4 cm³/10 min-   (4) polyethylene terephthalate (TR-8550T of Teijin Limited), (to be    referred to as PET-2 hereinafter), MVR value measured under a load    of 1.2 kg at 280° C. of 51.5 cm³/10 min    (II) Thermoplastic Resins (Component A-2)-   (1) polyphenylene ether (Zylon P-402 of Asahi Chemical Industry Co.,    Ltd.) (to be referred to as “PPE” hereinafter)-   (2) polycarbonate (Panlite L-1225WP of Teijin Chemicals Ltd.), (to    be referred to as “PC” hereinafter)-   (3) nylon 6 (NF-8020 of Teijin Limited) (to be referred to as “PA”    hereinafter)-   (4) ABS resin (Suntac UT-61 of Nippon A and L Co., Ltd.), (to be    referred to as “ABS” hereinafter)    (III) Organic Phosphorus Compounds (Component B-1)-   (1) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,    3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 1    {phosphorus-based compound of the above general formula (1) in which    X₁ and X₂ are the same, AL is a methylene group, Ar is a phenyl    group, and n is 1 (to be referred to as “FR-1” hereinafter)}-   (2) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,    3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 2    {phosphorus-based compound of the above general formula (1) in which    X₁ and X₂ are the same, AL is a methylene group, Ar is a phenyl    group, and n is 1 (to be referred to as “FR-2” hereinafter)}-   (3) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,    3,9-dibenzyl-3,9-dioxide having a high acid value synthesized in    Preparation Example 3 {phosphorus-based compound of the above    general formula (1) in which X₁ and X₂ are the same, AL is a    methylene group, Ar is a phenyl group, and n is 1 (to be referred to    as “FR-3” hereinafter)}-   (4) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,    3,9-dia-methylbenzyl-3,9-dioxide synthesized in Preparation Example    4 {phosphorus-based compound of the above general formula (1) in    which X₁ and X₂ are the same, AL is —CH(CH₃)—, Ar is a phenyl group,    and n is 1 (to be referred to as “FR-4” hereinafter)}-   (5) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,    3,9-di(2-phenylethyl)-3,9-dioxide synthesized in Preparation Example    5 {phosphorus-based compound of the above general formula (1) in    which X₁ and X₂ are the same, AL is an ethylene group, Ar is a    phenyl group, and n is 1 (to be referred to as “FR-5” hereinafter)}-   (6) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,    3,9-di(2-phenylethyl)-3,9-dioxide synthesized in Preparation Example    6 {phosphorus-based compound of the above general formula (1) in    which X₁ and X₂ are the same, AL is an ethylene group, Ar is a    phenyl group, and n is 1 (to be referred to as “FR-6” hereinafter)}-   (7) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,    3,9-bis(diphenylmethyl)-3,9-dioxide synthesized in Preparation    Example 7 {phosphorus-based compound of the above general    formula (1) in which X₁ and X₂ are the same, AL is a methine group,    Ar is a phenyl group, and n is 2 (to be referred to as “FR-7”    hereinafter)}-   (8) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,    3,9-bis(diphenylmethyl)-3,9-dioxide synthesized in Preparation    Example 8 {phosphorus-based compound of the above general    formula (1) in which X₁ and X₂ are the same, AL is a methine group,    Ar is a phenyl group, and n is 2 (to be referred to as “FR-8”    hereinafter)}-   (9) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,    3,9-bis(diphenylmethyl)-3,9-dioxide synthesized in Preparation    Example 9 {phosphorus-based compound of the above general    formula (1) in which X₁ and X₂ are the same, AL is a methine group,    Ar is a phenyl group, and n is 2 (to be referred to as “FR-9”    hereinafter)}    (IV) Organic Phosphorus Compound (Component B-2)    6H-benzo[c,e][1,2]oxaphospholin-6-one {compound of the above general    formula (2) in which R¹ to R⁸ are all hydrogen atoms, HCA of Sanko    Co., Ltd. (to be referred to as “FR-10” hereinafter)}    (V) Biscumyl Compound (Component B-3)    biscumyl {compound of the above general formula (3) in which R⁹ to    R¹⁸ are all hydrogen atoms, Nofmer BC 90 of NOF Corporation (to be    referred to as “BC” hereinafter)}    (VI) Other Organic Phosphorus Compounds-   (1) triphenyl phosphate {TPP of Daihachi Chemical Industry, Co.,    Ltd. (to be referred to as “TPP” hereinafter)}-   (2) 1,3-phenylenebis[di(2,6-dimethylphenyl)phosphate] {organic    phosphate compound of the above general formula (F-3) in which Ar⁴    is a phenylene group, and Q¹, Q², Q³ and Q⁴ are each a    2,6-dimethylphenyl group, Adecastaf FP-500 of Asahi Denka Kogyo K.K.    (to be referred to as “FP-500” hereinafter)}    (VII) Flame Retardancy Improving Resins (Component C)-   (1) polystyrene GPPS (styrene polymer of Wako Junyaku, Co., Ltd.)    (to be referred to as “C-1” hereinafter)-   (2) acrylonitrile-styrene copolymer (Stylac-AS783 of Asahi Chemical    Industry Co., Ltd.) (to be referred to as “C-2” hereinafter)-   (3) phenolic resin (PR-53195 of Sumitomo Bakelite Co., Ltd.) (to be    referred to as “C-3”)-   (4) epoxy resin (Epicoat 828 of Japan Epoxy Resin Co., Ltd.) (to be    referred to as “C-4”)    (VIII) Fillers (Component D)-   (1) glass milled fiber (PFE-301S of Nitto Boseki Co., Ltd.) (to be    referred to as “D-1” hereinafter)-   (2) glass chopped fiber (ECS03T-187H of Nippon Electric Glass Co.,    Ltd.) (to be referred to as “D-2” hereinafter)    (IX) Fluorine-Containing Resins (Component E)-   (1) polytetrafluoroethylene (Polyfuron MPAFA-500 of Daikin    Industries, Ltd.) (to be referred to as “E-1” hereinafter)-   (2) AS coated polytetrafluoroethylene (BLENDEX449 of GE Specialty    Chemicals Co., Ltd.) (to be referred to as “E-2” hereinafter)

The BLENDEX449 had a PTFE content of 50%, an acrylonitrile content of10% and a styrene content of 40%.

Examples a-1 to a-33, Examples b-1 to b-26, Examples c-1 to c-33,Examples d-1 to d-35, Examples e-1 to e-44, and Comparative Examples 1to 82

Components shown in Tables 1 to 6 were mixed together by a tumbler inamounts (parts by weight) shown in Tables 1 to 6 and pelletized by a 15mm-diameter double-screw extruder (KZW15 of Technovel Co., Ltd.).Compositions comprising a glass chopped fiber were pelletized by a 30mm-diameter single-screw extruder. The obtained pellets were dried with130° C. hot air by a drier for 4 hours. The dried pellets were molded byan injection molding machine (J75Si of Nippon Steel Co., Ltd.). Theevaluation results of molded plates are shown in Tables 1 to 6.

TABLES 1 Component Unit Ex. a-1 Ex. a-2 Ex. a-3 Ex. a-4 Ex. a-5 Ex. a-6Ex. a-7 Ex. a-8 Ex. a-9 Ex. a-10 Ex. a-11 A-1 Type PBT-1 PBT-1 PBT-2PBT-1 PBT-2 PET-1 PET-2 PBT-2 PBT-2 PBT-2 PBT-2 Component Parts byweight 100 100 100 100 100 100 100 100 100 100 100 A-2 Type — — — — — —— — — — — Component Parts by weight — — — — — — — — — — — B-1 Type FR-1FR-1 FR-1 FR-2 FR-2 FR-1 FR-1 FR-1 FR-1 FR-1 FR-1 Component Parts byweight  15  20   20  20  20  20  20  25  28.6  25  28.6 C Type — — — — —— — — — — — Component Parts by weight — — — — — — — — — — — D Type — — —— — — — D-1 D-1 D-2 D-2 Component Parts by weight — — — — — — —  25 42.9  25  42.9 E Type — — — — — — — — — — — Component Parts by weight —— — — — — — — — — — Flame Thickness of 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm retardancy specimen ULrating V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-2 V-2 Drips Seen Seen SeenSeen Seen Seen Seen Seen Seen Seen Seen Ignition of Not Not Not Not NotNot seen Not seen Not seen Not seen Seen Seen cotton seen seen seen seenseen L.O.I.  28.0  28.3  28.8  28.5  28.6  28.8  28.3  28.6  28.5  24.1 23.8 Ex. Ex. Ex. Ex. Ex. Component Unit a-12 a-13 a-14 a-15 a-16 Ex.a-17 Ex. a-18 Ex. a-19 Ex. a-20 Ex. a-21 Ex. a-22 A-1 Type PBT-1 PBT-1PBT-2 PBT-1 PBT-2 PBT-1 PBT-1 PBT-2 PBT-2 PBT-2 PBT-2 Component Parts byweight 100 100 100 100 100 95 90 71.4 71.4 71.4 71.4 A-2 Type — — — — —ABS ABS PPE PPE PPE PPE Component Parts by weight — — — — — 5 10 28.628.6 28.6 28.6 B-1 Type FR-1 FR-1 FR-1 FR-1 FR-1 FR-1 FR-1 FR-1 FR-1FR-1 FR-1 Component Parts by weight  10  15  15  15  15 30 30 28.6 42.928.6 42.9 C Type C-1 C-1 C-1 C-2 C-2 — — — — — — Component Parts byweight  1  1  1  1  1 — — — — — — D Type — — — — — — — D-2 D-2 D-2 D-2Component Parts by weight — — — — — — — 42.9 42.9 42.9 42.9 E Type — — —— — — — E-1 E-1 E-2 E-2 Component Parts by weight — — — — — — —  1.4 1.4  1.8  1.8 Flame Thickness of 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm retardancy specimen UL rating V-0V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Drips Seen Seen Seen Seen SeenSeen Seen Not seen Not seen Not seen Not seen Ignition of Not Not NotNot Not Not seen Not seen Not seen Not seen Not seen Not seen cottonseen seen seen seen seen L.O.I.  27.4  27.8  27.3  28.3  28.1 26.5 27.228.1 28.5 28.2 28.8 Ex. Ex. Ex. Ex. Ex. Component Unit a-23 a-24 a-25a-26 a-27 Ex. a-28 Ex. a-29 Ex. a-30 Ex. a-31 Ex. a-32 Ex. a-33 A-1 TypePBT-2 PBT-2 PBT-2 PBT-2 PBT-1 PBT-2 PBT-1 PBT-2 PBT-2 PBT-2 PBT-2Component Parts by weight 64.3 71.4 100 100 100 100 100 100 100 71.471.4 A-2 Type PC PA — — — — — — — PPE PPE Component Parts by weight 35.728.6 — — — — — — — 28.6 28.6 B-1 Type FR-1 FR-1 FR-1 FR-1 FR-1 FR-1 FR-2FR-2 FR-1 FR-1 FR-1 Component Parts by weight 42.9 42.9  60  60  20  20 20  20  28.6 42.9 42.9 C Type — — C-3 C-4 — — — — — — — Component Partsby weight — —  40  40 — — — — — — — D Type D-2 D-2 D-2 D-2 — — — — D-1D-2 D-2 Component Parts by weight 42.9 42.9  60  60 — — — —  42.9 42.942.9 E Type E-2 E-1 E-1 E-1 — — — — — E-1 E-2 Component Parts by weight 1.8  1.4  2  2 — — — — —  1.4  1.8 Flame Thickness of 1.6 mm 1.6 mm 1.6mm 1.6 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm retardancyspecimen UL rating V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Drips NotNot Not Not Seen Seen Seen Seen Seen Not seen Not seen seen seen seenseen Ignition of Not Not Not Not Not Not seen Not seen Not seen Not seenNot seen Not seen cotton seen seen seen seen seen L.O.I. 30.2 31.0  31.8 31.5  28.3  28.8  28.5  28.6  28.5 28.5 28.8 Ex. = Example

TABLES 2 Component Unit Ex. b-1 Ex. b-2 Ex. b-3 Ex. b-4 Ex. b-5 Ex. b-6Ex. b-7 Ex. b-8 Ex. b-9 A-1 Component Type PBT-1 PBT-2 PBT-2 PET-1 PET-2PBT-2 PBT-2 PBT-2 PBT-1 Parts by weight 100 100 100 100 100 100 100 100100 A-2 Component Type — — — — — — — — — Parts by weight — — — — — — — —— B-1 Component Type FR-4 FR-4 FR-4 FR-4 FR-4 FR-4 FR-4 FR-4 FR-4 Partsby weight  20  15  20  20  20  25  28.6  28.6  10 C Component Type — — —— — — — — C-1 Parts by weight — — — — — — — —  1 D Component Type — — —— — D-1 D-1 D-2 — Parts by weight — — — — —  25  42.9  42.9 — EComponent Type — — — — — — — — — Parts by weight — — — — — — — — — FlameThickness of specimen 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm1.6 mm 1.6 mm retardancy UL rating V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-2 V-0Drips Seen Seen Seen Seen Seen Seen Seen Seen Seen Ignition of cottonNot seen Not seen Not seen Not seen Not seen Not seen Not seen Seen Notseen L.O.I.  26.7  27.0  27.0  26.8  26.9  26.5  26.3  23.5  26.7Component Unit Ex. b-10 Ex. b-11 Ex. b-12 Ex. b-13 Ex. b-14 Ex. b-15 Ex.b-16 Ex. b-17 Ex. b-18 A-1 Component Type PBT-1 PBT-2 PBT-1 PBT-2 PBT-2PBT-2 PBT-2 PBT-2 PBT-2 Parts by weight 100 100 100 100 71.4 71.4 71.471.4 64.3 A-2 Component Type — — — — PPE PPE PPE PPE PC Parts by weight— — — — 28.6 28.6 28.6 28.6 35.7 B-1 Component Type FR-4 FR-4 FR-4 FR-4FR-4 FR-4 FR-4 FR-4 FR-4 Parts by weight  15  15  15  15 28.6 42.9 28.642.9 42.9 C Component Type C-1 C-1 C-2 C-2 — — — — — Parts by weight  1 1  1  1 — — — — — D Component Type — — — — D-2 D-2 D-2 D-2 D-2 Parts byweight — — — — 42.9 42.9 42.9 42.9 42.9 E Component Type — — — — E-1 E-1E-2 E-2 E-2 Parts by weight — — — —  1.4  1.4  1.8  1.8  1.8 FlameThickness of specimen 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm1.6 mm 1.6 mm retardancy UL rating V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0Drips Seen Seen Seen Seen Not seen Not seen Not seen Not seen Not seenIgnition of cotton Not seen Not seen Not seen Not seen Not seen Not seenNot seen Not seen Not seen L.O.I.  27  27.3  27.2  27.5 28.2 28.8 28.528.7 29.6 Component Unit Ex. b-19 Ex. b-20 Ex. b-21 Ex. b-22 Ex. b-23Ex. b-24 Ex. b-25 Ex. b-26 A-1 Component Type PBT-2 PBT-2 PBT-2 PBT-1PBT-2 PBT-2 PBT-2 PBT-2 Parts by weight 71.4 100 100 100 100 100 71.471.4 A-2 Component Type PA — — — — — PPE PPE Parts by weight 28.6 — — —— — 28.6 28.6 B-1 Component Type FR-4 FR-4 FR-4 FR-4 FR-4 FR-4 FR-4 FR-4Parts by weight 42.9  60  60  20  20  28.6 42.9 42.9 C Component Type —C-3 C-4 — — — — — Parts by weight —  40  40 — — — — — D Component TypeD-2 D-2 D-2 — — D-1 D-2 D-2 Parts by weight 42.9  60  60 — —  42.9 42.942.9 E Component Type E-1 E-1 E-1 — — — E-1 E-2 Parts by weight  1.4  2 2 — — —  1.4  1.8 Flame Thickness of specimen 1.6 mm 1.6 mm 1.6 mm 0.8mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm retardancy UL rating V-0 V-0 V-0 V-0 V-0V-0 V-0 V-0 Drips Not seen Not seen Not seen Seen Seen Seen Not seen Notseen Ignition of cotton Not seen Not seen Not seen Not seen Not seen Notseen Not seen Not seen L.O.I. 30.5  30.8  31.2  26.7  27.0  26.3 28.829.6 Ex. = Example

TABLES 3 Component Unit Ex. c-1 Ex. c-2 Ex. c-3 Ex. c-4 Ex. c-5 Ex. c-6Ex. c-7 Ex. c-8 Ex. c-9 Ex. c-10 Ex. c-11 A-1 Type PBT-1 PBT-1 PBT-2PBT-2 PBT-1 PBT-2 PET-1 PET-2 PBT-2 PBT-2 PBT-2 Component Parts byweight 100 100 100 100 100 100 100 100 100 100 100 A-2 Type — — — — — —— — — — — Component Parts by weight — — — — — — — — — — — B-1 Type FR-5FR-5 FR-5 FR-5 FR-6 FR-6 FR-5 FR-5 FR-5 FR-5 FR-5 Component Parts byweight  15  20  15  20  15  15  20  20  25  28.6  28.6 C Type — — — — —— — — — — — Component Parts by weight — — — — — — — — — — — D Type — — —— — — — — D-1 D-1 D-2 Component Parts by weight — — — — — — — —  25 42.9  42.9 E Type — — — — — — — — — — — Component Parts by weight — — —— — — — — — — — Flame Thickness of 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm retardancy specimen UL ratingV-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-2 Drips Seen Seen Seen SeenSeen Seen Seen Seen Seen Seen Seen Ignition of Not Not Not Not Not Notseen Not seen Not seen Not seen Not seen Seen cotton seen seen seen seenseen L.O.I.  27.5  27.8  27.3  28.3  27.4  27.5  27.0  26.8  28.3  28.0 23.2 Ex. Ex. Ex. Ex. Ex. Component Unit c-12 c-13 c-14 c-15 c-16 Ex.c-17 Ex. c-18 Ex. c-19 Ex. c-20 Ex. c-21 Ex. c-22 A-1 Type PBT-1 PBT-1PBT-2 PBT-1 PBT-2 PBT-1 PBT-1 PBT-2 PBT-2 PBT-2 PBT-2 Component Parts byweight 100 100 100 100 100 95 90 71.4 71.4 71.4 71.4 A-2 Type — — — — —ABS ABS PPE PPE PPE PPE Component Parts by weight — — — — —  5 10 28.628.6 28.6 28.6 B-1 Type FR-5 FR-5 FR-5 FR-5 FR-5 FR-5 FR-5 FR-5 FR-5FR-5 FR-5 Component Parts by weight  10  15  15  15  15 30 30 28.6 42.928.6 42.9 C Type C-1 C-1 C-1 C-2 C-2 — — — — — — Component Parts byweight  1  1  1  1  1 — — — — — — D Type — — — — — — — D-2 D-2 D-2 D-2Component Parts by weight — — — — — — — 42.9 42.9 42.9 42.9 E Type — — —— — — — E-1 E-1 E-2 E-2 Component Parts by weight — — — — — — —  1.4 1.4  1.8  1.8 Flame Thickness of 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm retardancy specimen UL rating V-0V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Drips Seen Seen Seen Seen SeenSeen Seen Not seen Not seen Not seen Not seen Ignition of Not Not NotNot Not Not seen Not seen Not seen Not seen Not seen Not seen cottonseen seen seen seen seen L.O.I.  27.3  28.1  27.8  28.5  28.3 27.2 26.828.5 28.8 28.3 28.8 Ex. Ex. Ex. Ex. Ex. Component Unit c-23 c-24 c-25c-26 c-27 Ex. c-28 Ex. c-29 Ex. c-30 Ex. c-31 Ex. c-32 Ex. c-33 A-1 TypePBT-2 PBT-2 PBT-2 PBT-2 PBT-1 PBT-2 PBT-1 PBT-2 PBT-2 PBT-2 PBT-2Component Parts by weight 64.3 71.4 100 100 100 100 100 100 100 71.471.4 A-2 Type PC PA — — — — — — — PPE PPE Component Parts by weight 35.728.6 — — — — — — — 28.6 28.6 B-1 Type FR-5 FR-5 FR-5 FR-5 FR-5 FR-5 FR-6FR-6 FR-5 FR-5 FR-5 Component Parts by weight 42.9 42.9  60  60  20  20 20  20  28.6 42.9 42.9 C Type — — C-3 C-4 — — — — — — — Component Partsby weight — —  40  40 — — — — — — — D Type D-2 D-2 D-2 D-2 — — — — D-1D-2 D-2 Component Parts by weight 42.9 42.9  60  60 — — — —  42.9 42.942.9 E Type E-2 E-1 E-1 E-1 — — — — — E-1 E-2 Component Parts by weight 1.8  1.4  2  2 — — — — —  1.4  1.8 Flame Thickness of 1.6 mm 1.6 mm 1.6mm 1.6 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm retardancyspecimen UL rating V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Drips NotNot Not Not Seen Seen Seen Seen Seen Not seen Not seen seen seen seenseen Ignition of Not Not Not Not Not Not seen Not seen Not seen Not seenNot seen Not seen cotton seen seen seen seen seen L.O.I. 30.0 31.5  31.2 30.8  27.8  28.3  27.5  27.8  28.0 28.8 30.0 Ex. = Example

TABLES 4 Component Unit Ex. d-1 Ex. d-2 Ex. d-3 Ex. d-4 Ex. d-5 Ex. d-6Ex. d-7 Ex. d-8 Ex. d-9 A-1 Component Type PBT-1 PBT-2 PBT-1 PBT-2 PBT-1PBT-2 PET-1 PET-2 PBT-2 Parts by weight 100 100 100 100 100 100 100 100100 A-2 Component Type — — — — — — — — — Parts by weight — — — — — — — —— B-1 Component Type FR-7 FR-7 FR-8 FR-8 FR-9 FR-9 FR-7 FR-7 FR-7 Partsby weight  20  20  20  20  20  20  20  20  25 C Component Type — — — — —— — — — Parts by weight — — — — — — — — — D Component Type — — — — — — —— D-1 Parts by weight — — — — — — — —  25 E Component Type — — — — — — —— — Parts by weight — — — — — — — — — Flame Thickness of specimen 1.6 mm1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm retardancy ULrating V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Drips Seen Seen Seen SeenSeen Seen Seen Seen Seen Ignition of cotton Not seen Not seen Not seenNot seen Not seen Not seen Not seen Not seen Not seen L.O.I.  28.0  28.8 27.8  28.5  27.7  28.3  28.5  28.3  28.5 Component Unit Ex. d-10 Ex.d-11 Ex. d-12 Ex. d-13 Ex. d-14 Ex. d-15 Ex. d-16 Ex. d-17 Ex. d-18 A-1Component Type PBT-2 PBT-2 PBT-2 PBT-1 PBT-2 PBT-1 PBT-2 PBT-2 PBT-2Parts by weight 100 100 100 100 100 100 100 71.4 71.4 A-2 Component Type— — — — — — — PPE PPE Parts by weight — — — — — — — 28.6 28.6 B-1Component Type FR-7 FR-7 FR-7 FR-7 FR-7 FR-7 FR-7 FR-7 FR-7 Parts byweight  28.6  25  28.6  15  15  15  15 28.6 42.9 C Component Type — — —C-1 C-1 C-2 C-2 — — Parts by weight — — — 1 1 1 1 — — D Component TypeD-1 D-2 D-2 — — — — D-2 D-2 Parts by weight  42.9  25  42.9 — — — — 42.942.9 E Component Type — — — — — — — E-1 E-1 Parts by weight — — — — — ——  1.4  1.4 Flame Thickness of specimen 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm retardancy UL rating V-0 V-2 V-2 V-0 V-0V-0 V-0 V-0 V-0 Drips Seen Seen Seen Seen Seen Seen Seen Not seen Notseen Ignition of cotton Not seen Seen Seen Not seen Not seen Not seenNot seen Not seen Not seen L.O.I.  28.3  22.8  22.5  28.2  28.5  28.5 28.8 28.0 28.5 Component Unit Ex. d-19 Ex. d-20 Ex. d-21 Ex. d-22 Ex.d-23 Ex. d-24 Ex. d-25 Ex. d-26 Ex. d-27 A-1 Component Type PBT-2 PBT-2PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 Parts by weight 71.4 71.4 64.371.4 71.4 100 100 100 100 A-2 Component Type PPE PPE PC PA PA — — — —Parts by weight 28.6 28.6 35.7 28.6 28.6 — — — — B-1 Component Type FR-7FR-7 FR-7 FR-7 FR-7 FR-7 FR-7 FR-7 FR-7 Parts by weight 28.6 42.9 42.928.6 42.9  60  60  60  60 C Component Type — — — — — C-3 C-4 C-3 C-4Parts by weight — — — — —  40  40  40  40 D Component Type D-2 D-2 D-2D-2 D-2 D-2 D-2 D-2 D-2 Parts by weight 42.9 42.9 42.9 42.9 42.9  60  60 60  60 E Component Type E-2 E-2 E-2 E-1 E-1 E-1 E-1 E-2 E-2 Parts byweight  1.4  1.4  1.4  1.4  1.4  2  2  2  2 Flame Thickness of specimen1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mmretardancy UL rating V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Drips Not seenNot seen Not seen Not seen Not seen Not seen Not seen Not seen Not seenIgnition of cotton Not seen Not seen Not seen Not seen Not seen Not seenNot seen Not seen Not seen L.O.I. 28.2 28.5 29.2 28.8 29.3  30.3  30.2 30.2  30.3 Component Unit Ex. d-28 Ex. d-29 Ex. d-30 Ex. d-31 Ex. d-32Ex. d-33 Ex. d-34 Ex. d-35 A-1 Component Type PBT-1 PBT-2 PBT-1 PBT-2PBT-2 PBT-2 PBT-2 PBT-2 Parts by weight 100 100 100 100 100 71.4 71.464.3 A-2 Component Type — — — — — PPE PPE PC Parts by weight — — — — —28.6 28.6 35.7 B-1 Component Type FR-7 FR-7 FR-8 FR-8 FR-7 FR-7 FR-7FR-7 Parts by weight  20  20  20  20  28.6 42.9 42.9 42.9 C ComponentType — — — — — — — — Parts by weight — — — — — — — — D Component Type —— — — D-1 D-2 D-2 D-2 Parts by weight — — — —  42.9 42.9 42.9 42.9 EComponent Type — — — — — E-1 E-2 E-2 Parts by weight — — — — —  1.4  1.4 1.4 Flame Thickness of specimen 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8mm 0.8 mm 0.8 mm retardancy UL rating V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0Drips Seen Seen Seen Seen Seen Not seen Not seen Not seen Ignition ofcotton Not seen Not seen Not seen Not seen Not seen Not seen Not seenNot seen L.O.I.  28.0  28.8  27.8  28.5  28.3 28.5 28.5 29.2 Ex. =Example

TABLES 5 Component Unit Ex. e-1 Ex. e-2 Ex. e-3 Ex. e-4 Ex. e-5 Ex. e-6Ex. e-7 Ex. e-8 Ex. e-9 Ex. e-10 Ex. e-11 A-1 Type PBT-1 PBT-1 PBT-1PBT-1 PBT-1 PBT-2 PBT-2 PET-2 PBT-2 PBT-2 PBT-1 Component Parts byweight 100 100 100 100 100 100 100 100 100 100 100 A-2 Type — — — — — —— — — — — Component Parts by weight — — — — — — — — — — — B-2 Type FR-10FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 ComponentParts by weight  6  8  10  12  15  6  8  10  12  15  8 B-3 Type BC BC BCBC BC BC BC BC BC BC BC Component Parts by weight  1  0.8  0.5  0.3  0.3 1  0.8  0.5  0.3  0.3  0.8 C Type — — — — — — — — — — — Component Partsby weight — — — — — — — — — — — D Type — — — — — — — — — — — ComponentParts by weight — — — — — — — — — — — E Type — — — — — — — — — — —Component Parts by weight — — — — — — — — — — — Flame Thickness of 1.6mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mmretardancy specimen UL rating V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0V-0 Drips Seen Seen Seen Seen Seen Seen Seen Seen Seen Seen SeenIgnition of Not Not Not Not Not Not Seen Not Seen Not Seen Not Seen NotSeen Not Seen cotton Seen Seen Seen Seen Seen L.O.I.  29.3  29.8  29.8 29.3  30.3  29.2  29.3  29.5  29.2  29.8  28.8 Ex. Ex. Ex. Ex. Ex.Component Unit e-12 e-13 e-14 e-15 e-16 Ex. e-17 Ex. e-18 Ex. e-19 Ex.e-20 Ex. e-21 Ex. e-22 A-1 Type PBT-1 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2PBT-2 PBT-1 PBT-1 PBT-2 PBT-1 Component Parts by weight 100 100 100 100100 100 100 100 100 100 100 A-2 Type — — — — — — — — — — — ComponentParts by weight — — — — — — — — — — — B-2 Type FR-10 FR-10 FR-10 FR-10FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 Component Parts by weight  10 8  10  10  10  10  10  10  15  10  10 B-3 Type BC BC BC BC BC BC BC BCBC BC BC Component Parts by weight  0.5  0.8  0.5  1  1  1  1  0.5  0.3 0.5  0.5 C Type — — — — — — — C-1 C-1 C-1 C-2 Component Parts by weight— — — — — — — 1 1 1 1 D Type — — — D-1 D-1 D-2 D-2 — — — — ComponentParts by weight — — —  25  42.9  25  42.9 — — — — E Type — — — — — — — —— — — Component Parts by weight — — — — — — — — — — — Flame Thickness of1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm1.6 mm retardancy specimen UL rating V-0 V-0 V-0 V-0 V-0 V-2 V-2 V-0 V-0V-0 V-0 Drips Seen Seen Seen Seen Seen Seen Seen Not Seen Not Seen NotSeen Not Seen Ignition of Not Not Not Not Not Seen Seen Not Seen NotSeen Not Seen Not Seen cotton Seen Seen Seen Seen Seen L.O.I.  29.3 29.0  29.2  29.8  29.5  23.2  22.5  30.2  30.5  30.3  30.5 Ex. Ex. Ex.Ex. Ex. Component Unit e-23 e-24 e-25 e-26 e-27 Ex. e-28 Ex. e-29 Ex.e-30 Ex. e-31 Ex. e-32 Ex. e-33 A-1 Type PBT-2 PBT-2 PBT-2 PBT-2 PBT-2PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 Component Parts by weight 100 71.471.4 71.4 71.4 71.4 71.4 100 100 100 100 A-2 Type — PPE PPE PC PC PA PA— — — — Component Parts by weight — 28.6 28.6 28.6 28.6 28.6 28.6 — — —— B-2 Type FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10FR-10 Component Parts by weight  10 20 20 20 20 20 20  40  40  40  40B-3 Type BC BC BC BC BC BC BC BC BC BC BC Component Parts by weight  0.5 1  1  1  1  1  1  2  2  2  2 C Type C-2 — — — — — — C-3 C-3 C-4 C-4Component Parts by weight  1 — — — — — —  40  40  40  40 D Type — D-2D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 Component Parts by weight — 42.942.9 42.9 42.9 42.9 42.9  60  60  60  60 E Type — E-1 E-2 E-1 E-2 E-1E-2 E-1 E-2 E-1 E-2 Component Parts by weight —  1.4  1.4  1.4  1.4  1.4 1.4  2  2  2  2 Flame Thickness of 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm retardancy specimen UL ratingV-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Drips Seen Not Not Not NotNot seen Not seen Not seen Not seen Not seen Not seen seen seen seenseen Ignition of Not Not Not Not Not Not seen Not seen Not seen Not seenNot seen Not seen cotton seen seen seen seen seen L.O.I.  30.5 29.2 29.529.0 29.8 30.2 30.3  30.0  29.8  29.2  29.5 Ex. Ex. Ex. Ex. Ex.Component Unit e-34 e-35 e-36 e-37 e-38 Ex. e-39 Ex. e-40 Ex. e-41 Ex.e-42 Ex. e-43 Ex. e-44 A-1 Type PBT-1 PBT-1 PBT-2 PBT-2 PBT-2 PBT-2PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 Component Parts by weight 100 100 100 100100 100 71.4 71.4 71.4 71.4 100 A-2 Type — — — — — — PPE PPE PC PA —Component Parts by weight — — — — — — 28.6 28.6 28.6 28.6 — B-2 TypeFR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10 FR-10Component Parts by weight  10  15  10  15  10  10 20 20 20 20  40 B-3Type BC BC BC BC BC BC BC BC BC BC BC Component Parts by weight  0.5 0.3  0.5  0.3  1  1  1  1  1  1  2 C Type — — — — — — — — — — C-3Component Parts by weight — — — — — — — — — —  40 D Type — — — — D-1 D-1D-2 D-2 D-2 D-2 D-2 Component Parts by weight — — — —  25  42.9 42.942.9 42.9 42.9  60 E Type — — — — — — E-1 E-2 E-2 E-1 E-1 ComponentParts by weight — — — — — —  1.4  1.4  1.4  1.4  2 Flame Thickness of0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm 0.8 mm0.8 mm retardancy specimen UL rating V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0V-0 V-0 Drips Seen Seen Seen Seen Seen Seen Not seen Not seen Not seenNot seen Not seen Ignition of Not Not Not Not Not Not seen Not seen Notseen Not seen Not seen Not seen cotton seen seen seen seen seen L.O.I. 29.8  30.3  29.5  29.8  29.8  29.5 29.2 29.5 29.8 30.2  30.0 Ex. =Example

TABLES 6 Component Unit C. Ex. 1 C. Ex. 2 C. Ex. 3 C. Ex. 4 C. Ex. 5 C.Ex. 6 C. Ex. 7 C. Ex. 8 C. Ex. 9 C. Ex. 10 C. Ex. 11 A-1 Type PBT-1PBT-2 PBT-1 PBT-2 PBT-1 PBT-1 PBT-2 PBT-2 PBT-1 PBT-1 PBT-2 ComponentParts by weight 100 100 100 100 100 100 100 100 100 100 100 A-2 Type — —— — — — — — — — — Component Parts by weight — — — — — — — — — — —Organic Type — — — — TPP TPP TPP TPP FP-500 FP-500 FP-500 phosphorousParts by weight — — — —  5  25  5  25  5  25  5 compound C Type — — — —— — — — — — — Component Parts by weight — — — — — — — — — — — D Type — —— — — — — — — — — Component Parts by weight — — — — — — — — — — — E Type— — — — — — — — — — — Component Parts by weight — — — — — — — — — — —Flame Thickness of 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6mm 1.6 mm 1.6 mm 1.6 mm retardancy specimen UL rating notV notV notVnotV V-2 V-2 V-2 V-2 V-2 V-2 V-2 Drips Seen Seen Seen Seen Seen SeenSeen Seen Seen Seen Seen Ignition of Seen Seen Seen Seen Seen Seen SeenSeen Seen Seen Seen cotton L.O.I.  23.2  22.2  21.3  20.7  25.1  26.1 25.3  26.0  24.8  25.9  24.8 C. Ex. C. Ex. C. Ex. C. Ex. C. Ex.Component Unit 12 13 14 15 16 C. Ex. 17 C. Ex. 18 C. Ex. 19 C. Ex. 20 C.Ex. 21 C. Ex. 22 A-1 Type PBT-2 PBT-1 PBT-1 PBT-2 PBT-2 PBT-1 PBT-1PET-2 PBT-2 PBT-1 PBT-1 Component Parts by weight 100 100 100 100 100100 100 100 100 100 100 A-2 Type — — — — — — — — — — — Component Partsby weight — — — — — — — — — — — Organic Type FP-500 FR-3 FR-3 FR-3 FR-3— — — — TPP TPP phosphorous Parts by weight  25  15  20  15  20 — — — — 20  20 compound C Type — — — — — C-1 C-2 C-1 C-2 C-1 C-2 ComponentParts by weight — — — — —  1  1  1  1  1  1 D Type — — — — — — — — — — —Component Parts by weight — — — — — — — — — — — E Type — — — — — — — — —— — Component Parts by weight — — — — — — — — — — — Flame Thickness of1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm1.6 mm retardancy specimen UL rating V-2 V-2 V-2 V-2 V-2 notV notV notVnotV V-2 V-2 Drips Seen Seen Seen Seen Seen Seen Seen Seen Seen SeenSeen Ignition of Seen Seen Seen Seen Seen Seen Seen Seen Seen Seen Seencotton L.O.I.  26.2  26.5  27.0  26.7  26.8  22.5  22.3  22.0  22.2 25.5  25.3 C. Ex. C. Ex. C. Ex. C. Ex. C. Ex. Component Unit 23 24 2526 27 C. Ex. 28 C. Ex. 29 C. Ex. 30 C. Ex. 31 C. Ex. 32 C. Ex. 33 A-1Type PBT-1 PBT-1 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PET-2 PBT-2 PBT-2 PBT-2Component Parts by weight 100 100 100 100 100 100 100 100 100 100 100A-2 Type — — — — — — — — — — — Component Parts by weight — — — — — — — —— — — Organic Type FP-500 FP-500 TPP TPP FP-500 FP-500 — — — — TPPphosphorous Parts by weight  20  20  20  20  20  20 — — — —  28.6compound C Type C-1 C-2 C-1 C-2 C-1 C-2 — — — — — Component Parts byweight  1  1  1  1  1  1 — — — — — D Type — — — — — — D-1 D-1 D-2 D-2D-2 Component Parts by weight — — — — — —  25  42.9  25  42.9  42.9 EType — — — — — — — — — — — Component Parts by weight — — — — — — — — — —— Flame Thickness of 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm1.6 mm 1.6 mm 1.6 mm 1.6 mm retardancy specimen UL rating V-2 V-2 V-2V-2 V-2 V-2 notV notV notV notV V-2 Drips Seen Seen Seen Seen Seen SeenSeen Seen Seen Seen Seen Ignition of Seen Seen Seen Seen Seen Seen SeenSeen Seen Seen Seen cotton L.O.I.  25.2  25.0  25.2  25.3  25.7  25.5 22.0  21.8  20.0  19.8  25.6 C. Ex. C. Ex. C. Ex. C. Ex. C. Ex.Component Unit 34 35 36 37 38 C. Ex. 39 C. Ex. 40 C. Ex. 41 C. Ex. 42 C.Ex. 43 C. Ex. 44 A-1 Type PBT-2 PBT-2 PBT-2 PBT-1 PBT-1 PBT-1 PBT-1PET-1 PBT-1 PBT-2 PBT-2 Component Parts by weight 100 100 100 95 90 9590 95 90 71.4 64.3 A-2 Type — — — ABS ABS ABS ABS ABS ABS PPE PPEComponent Parts by weight — — —  5 10  5 10  5 10 28.6 35.7 Organic TypeFP-500 TPP FP-500 — — TPP TPP FP-500 FP-500 — — phosphorous Parts byweight  28.6  28.6  28.6 — — 30 30 30 30 — — compound C Type — — — — — —— — — — — Component Parts by weight — — — — — — — — — — — D Type D-1 D-2D-2 — — — — — — D-2 D-2 Component Parts by weight  42.9  42.9  42.9 — —— — — — 42.9 42.9 E Type — — — — — — — — — E-1 E-1 Component Parts byweight — — — — — — — — —  1.4  1.4 Flame Thickness of 1.6 mm 1.6 mm 1.6mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm retardancyspecimen UL rating V-2 notV notV notV notV V-2 V-2 V-2 V-2 notV notVDrips Seen Seen Seen Seen Seen Seen Seen Seen Seen Not seen Not seenIgnition of Seen Seen Seen Seen Seen Seen Seen Seen Seen Not seen Notseen cotton L.O.I.  26.3  22.3  22.5 22.0 21.3 25.3 25.8 26.2 26.8 21.223.0 C. Ex. C. Ex. C. Ex. C. Ex. C. Ex. Component Unit 45 46 47 48 49 C.Ex. 50 C. Ex. 51 C. Ex. 52 C. Ex. 53 C. Ex. 54 C. Ex. 55 A-1 Type PBT-2PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 ComponentParts by weight 71.4 64.3 71.4 64.3 71.4 64.3 71.4 64.3 71.4 64.3 71.4A-2 Type PPE PPE PPE PPE PPE PPE PPE PPE PPE PPE PC Component Parts byweight 28.6 35.7 28.6 35.7 28.6 35.7 28.6 35.7 28.6 35.7 28.6 OrganicType — — TPP TPP FP-500 FP-500 TPP TPP FP-500 FP-500 — phosphorous Partsby weight — — 42.9 42.9 42.9 42.9 42.9 42.9 42.9 42.9 — comopound C Type— — — — — — — — — — — Component Parts by weight — — — — — — — — — — — DType D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 Component Parts byweight 42.9 42.9 42.9 42.9 42.9 42.9 42.9 42.9 42.9 42.9 42.9 E Type E-2E-2 E-1 E-1 E-1 E-1 E-2 E-2 E-2 E-2 E-1 Component Parts by weight  1.8 1.8  1.4  1.4  1.4  1.4  1.8  1.8  1.8  1.8  1.4 Flame Thickness of 1.6mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mmretardancy specimen UL rating notV notV V-2 V-2 V-2 V-2 V-2 V-2 V-2 V-2notV Drips Not Not Seen Seen Seen Seen Seen Seen Seen Seen Seen seenseen Ignition of Not Not Seen Seen Seen Seen Seen Seen Seen Seen Seencotton seen seen L.O.I. 21.0 23.2 25.3 26.9 25.6 27.3 25.4 27.1 25.427.1 20.8 C. Ex. C. Ex. C. Ex. C. Ex. C. Ex. Component Unit 56 57 58 5960 C. Ex. 61 C. Ex. 62 C. Ex. 63 C. Ex. 64 C. Ex. 65 C. Ex. 66 A-1 TypePBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2Component Parts by weight 64.3 71.4 64.3 64.3 64.3 64.3 64.3 71.4 64.371.4 64.3 A-2 Type PC PC PC PC PC PC PC PA PA PA PA Component Parts byweight 35.7 28.6 35.7 35.7 35.7 35.7 35.7 28.6 35.7 28.6 35.7 OrganicType — — — TPP FP-500 TPP FP-500 — — — — Phosphorous Parts by weight — —— 42.9 42.9 42.9 42.9 — — — — compound C Type — — — — — — — — — — —Component Parts by weight — — — — — — — — — — — D Type D-2 D-2 D-2 D-2D-2 D-2 D-2 D-2 D-2 D-2 D-2 Component Parts by weight 42.9 42.9 42.942.9 42.9 42.9 42.9 42.9 42.9 42.9 42.9 E Type E-1 E-2 E-2 E-1 E-1 E-2E-2 E-1 E-1 E-2 E-2 Component Parts by weight  1.4  1.8  1.8  1.4  1.4 1.8  1.8  1.4  1.4  1.8  1.8 Flame Thickness of 1.6 mm 1.6 mm 1.6 mm1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm retardancyspecimen UL rating notV notV notV V-2 V-2 V-2 V-2 notV notV notV notVDrips Seen Seen Seen Seen Seen Seen Seen Seen Seen Seen Seen Ignition ofSeen Seen Seen Seen Seen Seen Seen Seen Seen Seen Seen cotton L.O.I.21.3 21.1 21.3 28.2 28.3 28.5 28.7 21.5 21.8 21.7 22.2 C. Ex. C. Ex. C.Ex. C. Ex. C. Ex. Component Unit 67 68 69 70 71 C. Ex. 72 C. Ex. 73 C.Ex. 74 C. Ex. 75 C. Ex. 76 C. Ex. 77 A-1 Type PBT-2 PBT-2 PBT-2 PBT-2PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 Component Parts by weight 64.364.3 64.3 64.3 100 100 100 100 100 100 100 A-2 Type PA PA PA PA — — — —— — — Component Parts by weight 35.7 35.7 35.7 35.7 — — — — — — —Organic Type TPP FP-500 TPP FP-500 — — — — TPP TPP TPP phosphorous Partsby weight 42.9 42.9 42.9 42.9 — — — —  60  60  60 compound C Type — — —— C-3 C-4 C-3 C-4 C-3 C-4 C-3 Component Parts by weight — — — —  40  40 40  40  40  40  40 D Type D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2Component Parts by weight 42.9 42.9 42.9 42.9  60  60  60  60  60  60 60 E Type E-1 E-1 E-2 E-2 E-1 E-1 E-2 E-2 E-1 E-1 E-2 Component Partsby weight  1.4  1.4  1.8  1.8  2  2  2  2  2  2  2 Flame Thickness of1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm 1.6 mm1.6 mm retardancy specimen UL rating V-2 V-2 V-2 V-2 notV notV notV notVV-2 V-2 V-2 Drips Seen Seen Seen Seen Seen Seen Seen Seen Seen Seen SeenIgnition of Seen Seen Seen Seen Seen Seen Seen Seen Seen Seen Seencotton L.O.I. 26.3 26.7 26.3 26.8  22.0  22.3  22.2  21.8  26.8  26.7 26.5 Component Unit C. Ex. 78 C. Ex. 79 C. Ex. 80 C. Ex. 81 C. Ex. 82A-1 Component Type PBT-2 PBT-2 PBT-2 PBT-2 PBT-2 Parts by weight 100 100100 100 100 A-2 Component Type — — — — — Parts by weight — — — — —Organic Type TPP FP-500 FP-500 FP-500 FP-500 phosphorous Parts by weight 60  60  60  60  60 compound C Component Type C-4 C-3 C-4 C-3 C-4 Partsby weight  40  40  40  40  40 D Component Type D-2 D-2 D-2 D-2 D-2 Partsby weight  60  60  60  60  60 E Component Type E-2 E-1 E-1 E-2 E-2 Partsby weight  2  2  2  2  2 Flame Thickness of specimen 1.6 mm 1.6 mm 1.6mm 1.6 mm 1.6 mm retardancy UL rating V-2 V-2 V-2 V-2 V-2 Drips SeenSeen Seen Seen Seen Ignition of cotton Seen Seen Seen Seen Seen L.O.I. 26.8  27.0  26.5  26.8  27.2 C. Ex. = Comparative Example

As for the compositions of Examples a-1 to a-3, a-6 and a-7 in Table 1,0.8 mm-thick transparent test specimens were obtained by molding at acylinder temperature of 270° C. and a mold temperature of 0° C. inExamples a-1 to a-3 and at a cylinder temperature of 250° C. and a moldtemperature of 30° C. in Examples a-6 and a-7. When the total lighttransmittances of these test specimens were measured, they were 85%(a-1), 84% (a-2), 84% (a-3), 89% (a-6) and 90% (a-7).

MVR's measured under a load of 3.8 kg at 230° C. of the pellets ofExamples a-1 and a-2 were 24.5 cm³/10 min and 24.3 cm³/10 min,respectively, which means that they were excellent in fluidity with highpractical applicability.

Further, when MVR's of the pellets of Examples a-1 and a-2 were measuredafter they were treated at 130° C. for 24 hours, they were 24.1 cm³/10min and 25.2 cm³/10 min, respectively, which means that resindecomposition did not take place. ΔY of the pellet of Example a-1 was1.6% and ΔY of the pellet of Example a-2 was 3.7%.

Meanwhile, when MVR's of the pellets of Comparative Examples 13 and 14in Table 6 were measured before and after they were heated at 130° C.for 24 hours, they were 50.8 cm³/10 min and 52.5 cm³/10 min beforeheating and 62.5 cm³/10 min and 65.3 cm³/10 min after heating,respectively, which means that resin decomposition was promoted. ΔY ofthe pellet of Comparative Example 13 was 23.0% and ΔY of the pellet ofComparative Example 14 was 24.4%.

As for the compositions of Examples b-1 to b-5 in Table 2, 0.8 mm-thicktransparent test specimens were obtained by molding at a cylindertemperature of 270° C. and a mold temperature of 0° C. in Examples b-1to b-3 and at a cylinder temperature of 250° C. and a mold temperatureof 30° C. in Examples b-4 and b-5. When the total light transmittancesof the test specimens were measured, they were 84% (b-1), 83% (b-2), 84%(b-3), 90% (b-4) and 92% (b-5).

MVR measured under a load of 3.8 kg at 230° C. of the pellet of Exampleb-1 was 27.5 cm³/10 min, which means that it was excellent in fluiditywith high practical applicability. When MVR of the pellet of Example b-1was measured after it was heated at 130° C. for 24 hours, it was 26.8cm³/10 min, which means that resin decomposition did not take place. ΔYof the pellet of Example b-1 was 2.5%.

As for the compositions of Examples c-1 to c-4, c-7 and c-8 in Table 3,0.8 mm-thick transparent test specimens were obtained by molding at acylinder temperature of 270° C. and a mold temperature of 0° C. inExamples c-1 to c-4 and at a cylinder temperature of 250° C. and a moldtemperature of 30° C. in Examples c-7 and c-8. When the total lighttransmittances of the test specimens were measured, they were 87% (c-1),86% (c-2), 85% (c-3), 93% (c-7) and 95% (c-8).

MVR's measured under a load of 3.8 kg at 230° C. of the pellets ofExamples c-1 and c-2 were 30.0 cm³/10 min and 36.4 cm³/10 min,respectively, which means that they were excellent in fluidity with highpractical applicability.

When MVR's of the pellets of Examples c-1 and c-2 were measured afterthey were heated at 130° C. for 24 hours, they were 30.5 cm³/10 min and35.6 cm³/10 min, which means that resin decomposition did not takeplace. ΔY of the pellet of Example c-1 was 1.7%, and ΔY of the pellet ofExample c-2 was 2.2%.

MVR measured under a load of 3.8 kg at 230° C. of the pellet of Exampled-1 in Table 4 was 13.4 cm³/10 min, which means that it was excellent influidity with high practical applicability. When MVR of the pellet ofExample d-1 was measured after it was heated at 130° C. for 24 hours, itwas 13.8 cm³/10 min, which means that resin decomposition did not takeplace. ΔY of the pellet of Example d-1 was 3.0%.

EFFECT OF THE INVENTION

The flame retardant resin composition and molded article formedtherefrom of the present invention have the following advantagescompared with the flame retardant polyester resin composition of theprior art.

(i) A polyester resin composition having high flame retardancy isobtained without using substantially a halogen-containing flameretardant.

(ii) Since an organic phosphorus compound as a flame retardant has anexcellent flame retarding effect for a polyester resin, V-2 flameretardancy is achieved with a relatively small amount of the organicphosphorus compound. A composition having V-0 flame retardancy is easilyobtained. That is, a V-0 flame retardant composition is obtained with arelatively simple composition without the need of adding a large numberof components for attaining V-0 rating.(iii) A polyester composition having V-0 flame retardancy is easilyobtained by combining an organic phosphorus compound as a flameretardant with a specific flame retardancy improving resin and blendinga relatively small amount of the organic phosphorus compound.(iv) There is obtained a resin composition which rarely experiences thedeterioration of a polyester resin and has excellent heat stability atthe time of molding a polyester resin or using a molded article due tothe structure and characteristic properties of an organic phosphoruscompound used as a flame retardant. Therefore, a composition having goodbalance among flame retardancy, mechanical strength and heat stabilityis obtained.(v) Since an organic phosphorus compound as a flame retardant isachromatic and compatible with a polyester resin, a molded articlehaving excellent transparency can be obtained. A polyester resin moldedarticle having V-0 flame retardancy and excellent transparency has notbeen available on the market.

1. A flame retardant resin composition consisting essentially of: (A)100 parts by weight of the total of resin components (components A)which include at least 60 wt % of an aromatic polyester resin; (B) 1 to100 parts by weight of an organic phosphorus compound represented by thefollowing general formula (1-a) and having an acid value of 0.7 mgKOH/gor less (component B-1-a); (C) 0 to 50 parts by weight of a flameretardancy improving resin (component C); and (D) 0 to 200 parts byweight of a filler (component D):


2. The flame retardant resin composition of claim 1, wherein thearomatic polyester resin (A) is at least one selected from the groupconsisting of polyethylene terephthalate resin, polybutyleneterephthalate resin, polyethylene naphthalate resin, polybutylenenaphthalate resin, polcyclohexanedimethyl terephthalate resin,polytrimethylene terephthalate resin and polytrimethylene naphthalateresin.
 3. The flame retardant resin composition of claim 1, wherein thearomatic polyester resin (A) is at least one selected from the groupconsisting of polyethylene terephthalate resin, polybutyleneterephthalate resin and polyethylene naphthalate resin.
 4. The flameretardant resin composition of claim 1, wherein the components A consistof 60 to 100 parts by weight of an aromatic polyester resin (componentA-1) and 40 to 0 part by weight of at least one thermoplastic resin(component A-2) selected from the group consisting of polyphenyleneether resin, polycarbonate resin, polyamide resin, polyolefin resin,styrene-based resin, polyphenylene sulfide resin and polyether imideresin.
 5. The flame retardant resin composition of claim 1, wherein theorganic phosphorus compound (B) (component B-1-a) has an acid value of0.5 mgKOH/g or less.
 6. The flame retardant resin composition of claim1, wherein the organic phosphorus compound (B) (component B-1-a) has anHPLC purity of at least 90%, when measured by the following method: aDevelosil ODS-7 column having a length of 300 mm and a diameter of 4 mmof Nomura Kagaku Co., Ltd. is used; the column temperature is 40° C.;the solvent is a mixed solution of acetonitrile and water in a volumeratio of 6:4 and is injected in an amount of 5 μl; and a UV-260 nmdetector is used.
 7. The flame retardant resin composition of claim 1,which further consists essentially of at least one compound selectedfrom the group consisting of compounds of the following formulas (1-b)to (1-d):


8. The flame retardant resin composition of claim 1 which comprises 5 to90 parts by weight of the component B-1-a based on 100 parts by weightof the total of the components A.
 9. The flame retardant resincomposition of claim 1, wherein the flame retardancy improving resin (C)(component C) is at least one selected from the group consisting ofphenolic resin, epoxy resin and styrene-based resin and contained in anamount of 0.01 to 45 parts by weight based on 100 parts by weight of thetotal of the components A.
 10. The flame retardant resin composition ofclaim 1 which comprises the filler (D) in an amount of 1 to 150 parts byweight based on 100 parts by weight of the total of the components A.11. The flame retardant resin composition of claim 1 which containssubstantially no halogen.
 12. The flame retardant resin composition ofclaim 1 which provides a 1.6 mm-thick molded article having UL-94 V-0flame retardancy.
 13. The flame retardant resin composition of claim 1which provides a 0.8 mm-thick molded article having UL-94 V-0 flameretardancy.
 14. The flame retardant resin composition of claim 1 whichhas a heat stability (MVR change rate) of 20% or less, when MVR changerate is measured by the following method: a pellet is treated at 130° C.for 24 hours; MVR of the pellet is measured under a load of 3.8 kg at230° C. before and after the treatment to obtain its change rate fromthe expressionΔY=(|Y ₂ −Y ₁ |/Y ₁)×100(%) Y₁: MVR before treatment (cm³/10 min) Y₂:MVR after treatment (cm³/10 min).
 15. A transparent and flame retardantresin composition consisting essentially of: (A) 100 parts by weight ofthe total of resin components (components A) which include at least 60wt % of an aromatic polyester resin; (B) 1 to 100 parts by weight of anorganic phosphorus compound represented by the following general formula(1-a) and having an acid value of 0.7 mgKOH/g or less (component B-1-a);(C) 0 to 50 parts by weight of a flame retardancy improving resin(component C); and (E) 0 to 10 parts by weight of a fluorine-containingresin (component E), and having a total light transmittance of 80% ormore:


16. A method of imparting flame retardancy to an aromatic polyesterresin, which comprises mixing an effective amount of an organicphosphorus compound represented by formula (1-a) and having an acidvalue of 0.7 mgKOH/g or less (component B-1-a) with the aromaticpolyester resin,


17. A molded article formed from the flame retardant resin compositionof claim
 1. 18. A molded article formed from the flame retardant resincomposition of claim 15.